Intrachromoleucospheruloid pigment compositions and processes for producing the same

ABSTRACT

An intrachromoleucospheruloid pigment composition and a process for producing the same; the intrachromoleucospheruloid pigment composition consisting essentially of spheruloids of essentially transparent organic polymer material, preferably cross-linked to essential insolubility in any physical solvent, having primary particles of an average size not exceeding 4 microns in diameter which have embedded therein particulate pigment composition consisting essentially of (a) organic color pigment material having primary particles of an average particle size not exceeding 0.2 micron and preferably below 0.02 micron in diameter in combination with (b) inorganic leuco pigment material consisting essentially of inorganic white and/or transparent white pigment material having a different refractive index from that of element (a) and primary particles not exceeding 0.2 micron and preferably between 0.2 and 0.1 micron in diameter. In the process for its production (a) the organic color pigment material is reduced to an average particle size of 0.2 micron or less, (b) the inorganic leuco pigment material is reduced to an average particle size of 0.2 micron or less, (c) the combined organic and inorganic leuco pigment materials (a) and (b) are then included in an emulsion polymerization of monomer material preferably comprising an effective quantity of cross-linking agent, and the polymerization is conducted to produce emulsion polymer of an average particle size not exceeding 4 microns in diameter, having embedded therein the still smaller organic color and inorganic leuco pigment particles. Cooperative features are also disclosed.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to colored pigment compositions of highrefractive index and hue intensity and physical properties, and aimsgenerally to improve the same and provide novel processes for theproduction thereof.

2. Description of the Prior Art

In the prior art it has been well known to produce the so-called "Laked"or "Extended" pigment colors, usually by precipitation of a watersoluble organic dye or pigment color base onto an inert and inherentlycolorless or white substrate material to either impart useful pigmentaryproperties to an otherwise unsuitable organic or inorganic colormaterial or to give improved physical properties to an already usefulcolor. Such treatments and combinations thereof included the enclosingor encapsulation of inorganic color material such as the lead chromateyellows with a siliceous envelope or encapsulation, to inhibit or reducetheir toxicological properties, and also includes the laking of azo andrelated organic pigments on such insoluble substrate material asalumina, blanc fixe and similar compositions.

All these earlier methods simply dilute the color portion of theresulting pigment composition and essentially provide a wet or drydispersion of the color pigment or chromogen containing part, intimatelyadmixed with the inert or extender portion of the composition.

Such "Laked" or "Extended" colors are usually considerably duller andmuch weaker tinctorially than the original chromogen containingconstituent, and furthermore are not infrequently themselves easilydisunited into the separate components of said composition. This isespecially true concerning the use of mixtures of organic color pigmentswhere two or more are combined together to produce a shade differentfrom either alone.

SUMMARY OF THE INVENTION

In the conventional practices above described certain combinations ofcolored or chromogen containing organic pigments with opaque white ortransparent white, i.e. leuco pigments have been achieved either throughthe use of conventional laking techniques necessitating the use of theorganic colors in their water soluble form, or by simple physicaldilution of the organic color pigment with the colorless inorganicpigment material. Both pratices while extensively used in the art todayrepresent little or no improvement over the state of the art which hasexisted from almost the first use of color for decorative purposes. Thepresent invention aims to eliminate the inherent inefficiency of thesepractices by first reducing both the organic color pigment and theinorganic leuco pigment, either separately or together, to below thenormal limits of conventional pigmentary size, forming a composite ofsaid organic color and inorganic leuco pigment material wherein saidreduced particles of color pigment as one component and of said leucopigment as another component are wedded to one another to form compositeparticles essentially comprising both components either during orsubsequent to said reduction in particle size, and then by surroundingsaid composite particles with spheruloid bodies of essentiallytransparent polymer material, insoluble in the environment of intendeduse, and which differ in refractive index from said organic andinorganic pigments embedded therein, so that by light refraction theycan enhance to the viewer the apparent size and pigmentary power of saidembedded particles.

In forming the composite particles from the two components thereof,organic color pigment and inorganic leuco pigment, provision is requiredfor the wedding of the two components. This may be effected byco-micronizing the particles so that freshly fractured areas of onecomponent, with the electrical charges associated therewith, are broughtinto intimate contact with the freshly fractured areas of the othercomponent, whereby the particles of the respective components are weddedto each other. Such wedding may also be effected by separatelymicronizing the organic and inorganic components in aqueous media withthe aid of predominantly nonionic or weakly anionic surface activeagents such as e.g. Triton X405 and Alipal CO433, containingrespectively a small proportion, in the range of 1-10% by weight of thetotal surface active agent, of ionic surface active agents of oppositepolarity, preferably anionic in the case of the organic color pigmentand cationic in the case of the inorganic pigment, and then combiningand co-micronizing the so formed dispersions, whereby the anionicallyand cationically prepared pigment particles are intimately attracted toeach other and become wedded in the liquid medium to form compositeparticles which remain dispersed in the liquid medium with the aid ofthe nonionic emulsifier which is employed in sufficient amount tomaintain such composite dispersion when formed. The wedding of theorganic color pigment to the inorganic leuco pigment to form thecomposite pigment particles, may be aided when necessary or desired,depending on the particular pigments employed, by the co-grinding withthe combined components of 0 to an equal weight based on the inorganicpigment, of suitable bonding agent and/or nitrogenous material selectedfrom the classes hereinafter set forth.

In a preferred embodiment of the invention a process is provided forproducing insoluble intrachromoleucospheruloid of high refractive index,which process comprises, in combination: (a) providing in liquid medium,dispersed in said medium with 0-100% by weight of the total surfaceactive agent set forth in clause (c) of this paragraph, a particulatecomposite chromoleuco pigment composition consisting essentially oforganic color pigment material intimately combined with and wedded toinorganic leuco pigment material, the weight ratio of said organic colorpigment material to said inorganic leuco pigment material lying in therange of 100:1 to 1:100, dry basis, said chromoleuco pigment compositionbeing essentially insoluble in water and having primary particles of anaverage size less than 0.2 micron in diameter; (b) forming an aqueousemulsion polymerization system consisting essentially of (1) thecomposition of (a), (2) the balance, if any, of 100% of the total ofsurface active agent material set forth in (c), (3) monomer materialselected in a ratio of said monomer material to said chromoleuco pigmentcomposition lying in the range of 100:1 to 1:20 by weight, said monomermaterial consisting essentially of ethylenically unsaturated monomermaterial selected from the class consisting of (i) monomerspolymerizable through a single ethylenically unsaturated group in theamount of 0% to 99.8% by weight of said monomer material and (ii)monomers polymerizable through a plurality of ethylenically unsaturatedgroups in an amount, in the range of 0.2 to 100% by weight of saidmonomer material, sufficient to produce polymer cross-linked toessential insolubility in any physical solvent and (4) emulsionpolymerization initiator in an effective amount in the range of 0.2% to10% by weight of the said monomer material, dispersed in an aqueousmedium; (c) the ratio of the total of the surface active agent materialpresent after (b) to said composite particulate pigment compositionlying in the range of 2:1 to 1:40 by weight, and said total of surfaceactive agent material being selected from the class of polymeric andnonpolymeric surface active agents and combinations thereof capable ofeffecting emulsion polymerization in the said system of the selectedethylenically unsaturated monomer material to yield polymer particleswith the composite pigment composition provided in step (a) embeddedtherein; (d) effecting emulsion polymerization in said system atsufficient temperatures in the range of 0°-200° C. for sufficient timein the range of a few minutes to 24 hours to permit the polymerizationto proceed far enough in the range of from 50 to 100% conversion byweight of said monomer material to produce as an aqueous dispersion anintrachromoleucospheruloid pigment composition consisting essentially ofspheruloids of organic polymer material, cross-linked to essentialinsolubility in any physical solvent, having primary particles of anaverage size not exceeding 4 microns in diameter, and having embeddedtherein the still smaller size particles of said composite chromoleucopigment composition, and (e) recovering said intrachromoleucospheruloidpigment composition.

In this embodiment the monomer material may comprise several portionsadded sequentially, at least one of the portions comprisingcross-linking monomer as set forth and the cross-linking monomer mayconsist essentially of material copolymerizable with vinyl monomer, andmay be wholly or partially selected from the unsaturated conjugateddrying oils and their acids and derivatives thereof in the ratio to thevinyl and/or other copolymerizable monomer of 0.2:99.8 to 20:80 byweight.

The product of this preferred embodiment is particularly desirablebecause we have discovered that it may be modified to be soft powderingas hereinafter disclosed whereas said technique is inapplicable tononcross-linked oil soluble polymers.

For special purposes and with less general advantage a less preferredembodiment of the invention may be employed wherein the monomer materialin step (b) consists essentially of ethylenically unsaturated monomermaterial selected from the class consisting of monomers polymerizablethrough a single ethylenically unsaturated group, to produce spheruloidsconsisting of essentially noncross-linked organic polymer material, withlimitation of the special utility of the product to environments inwhich its polymer portion is essentially insoluble.

We have found it to be essential to the present invention to reduce theorganic color pigment to an average particle size essentially below 0.2micron and preferably below 0.02 micron in diameter, and to reduce theinorganic leuco pigment to below 0.2 micron and preferably between 0.2and 0.1 micron in diameter, said values being well below the optimumpigmentary ranges normally associated with said pigment materials and toeffect wedding of the microground color and leucopigment to form acomposite chromoleuco pigment; and that it is then possible to embedsuch ultra fine composite chromoleuco pigment material withintransparent polymer spheruloids insoluble in the environment of intendeduse, preferably nonfusible at the temperature of intended use, and whichdiffer in refractive index from that of the embedded composite pigmentmaterial, and which are of not more than 4 microns average particle sizeto obtain the new and useful characteristics of the present invention.The reduction in pigment particle size to such ultra fineness may beeffected by micronizing in a liquid medium, e.g. in a ball mill orpreferably a sand mill. The liquid medium may be an aqueous solution ofdispersing agent preferably selected from those known to be suitable foreffecting emulsion polymerization, or it may be a liquid body of monomermaterial with or without such dispersing agent and with or without avolatile organic diluent miscible with said monomer, the monomermaterial being suitable for polymerization in the formation of the finalproduct.

The organic pigment color starting material may be in any convenientlyavailable form, either as wet presscake or dry material as iscommercially available; as also may be the inorganic leuco pigmentmaterial such as are described more fully in the definition of termselsewhere in this application and in our co-pending application Case90-E.

Also the organic color and inorganic leuco pigments may be either groundseparably and combined prior to the polymerization step or may beco-ground in which case the inorganic leuco pigment may be considered asa grinding assistant in the reduction of particle size of the softermore easily ground organic color pigment material, subject to the abovenamed requirements for effecting wedding of the micronized organic colorpigment and the micronized inorganic leuco pigment to form the compositechromoleuco pigment.

The polymerization of the monomer or monomers with the compositechromoleuco pigment composition is carried out in the presence ofsufficient emulsifier material to effect emulsion polymerization of themonomer material, and the nature and quantity of initiator andemulsifier, the degree of conversion of monomer to polymer, and thetemperature of polymerization are selected to produceintrachromoleucospheruloid pigment having primary particles of anaverage size not exceeding 4 microns so that the potential colorstrength available may be fully developed and retained in the finishedproduct. The amount of dispersant or surface active agent employed inaqueous micronizing of the pigment material can be as low as isconsistent with reduction of the particle size to the desired level andthe maintenance of its size stability.

During the emulsion polymerization functional groups may be introducedto aid in the fixation of the intrachromoleucospheruloid pigmentcomposition to the environment of intended use by physical and/orchemical bonding, either by selection of the monomer or monomers used,or by selection of the emulsifier or emulsifiers, particularly those ofa polymeric nature, which become association with theintrachromoleucospheruloid pigment particles, or may be later introducedby means of graft polymerization techniques.

Whether prepared by the preferred or less preferred embodiments theproduct may be recovered in step (e) in latex form, in presscake form,or in bulk dried or in spray dried form, and may be used in vehicles inwhich the polymer portion of the product is insoluble, and as abovenoted, when the polymer portions of the product are cross-linked toessential insolubility in any physical solvent the products may berecovered in soft powdered form and/or be used in any suitable vehicle.

Thus as just described, the polymer portion of theintrachromoleucospheruloid pigment composition of applicants' inventionis formed to be insoluble in the environment of intended use, and in thepreferred practice of the invention is cross-linked to insolubility inall physical solvents, although in certain instances such cross-linkingmay be omitted.

BRIEF DESCRIPTION OF DRAWINGS

In the accompanying drawings illustrative of preferred embodiments ofthis invention:

FIG. 1 is a process flow diagram of the procedure for production ofintrachromoleucospheruloid pigments in latex and/or other forms.

FIGS. 2, 3, 4, and 5 are detail flow diagrams of processes forconverting the aqueous dispersion of intrachromoleucospheruloid pigmentcomposition produced in FIG. 1 into other forms such as wet presscake,dry powder or soft powder form.

GENERAL PROCEDURE

The general procedures for preparing intrachromoleucospheruloid pigmentcompositions in accordance with the process of the invention areillustrated in the drawings. In these procedures (FIG. 1) (a) a pigmentcomposition 8 is first provided consisting essentially of liquid havingdispersed therein micronized organic color pigment and micronizedinorganic leuco pigment, essentially insoluble in said liquid, andessentially wedded together.

As shown in the drawing and heretofore explained the dispersion ofcomposite chromoleuco pigment composition may either be produced byco-micronizing and wedding the said organic and inorganic pigmentcomponents or they may be micronized separately and combined and weddedto form the pigment composition 8, it being readily understood to thosefamiliar with the art that it is necessary when separate micronizing iseffected that the liquid medium employed in each case be compatible withthe other.

When an aqueous micronizing liquid 3 is employed, it comprises surfaceactive agent material 2 which stabilizes the dispersion of themicronized pigment material in said aqueous phase, in which the pigmentis so finely divided as to have an average particle size below the usualpigmentary range. As shown in FIG. 1 the micronizing may be accomplishedby charging to a micronizing apparatus 5, e.g. a ball mill or preferablya sand grinder, a slurry 4, of pigment material e.g. 1, organic colorpigment, 1a, inorganic leuco pigment or a combination of 1 and 1a, withsufficient water 3 to facilitate the grinding and sufficient surfaceactive agent material 2 to stabilize the dispersion to be produced. Thecharge of slurry 4 is then micronized as at 5 until the pigmentparticles are so finely divided that the average particulate entitiesthereof have an average particle size of less than 0.2 micron and in thecase of the organic color pigment preferably of less than 0.02 micronand then separated as at 6 from the micronizing medium 6a, e.g. sand, tosupply the chromoleuco composite pigment dispersion 8. In the aqueousmicronizing procedure the ratio of pigment material to water to obtainefficient grinding should be in the range of 20:80 to 30:70 and theratio of surface active agent material to water should be in the rangeof 5:95 to 20:80 parts by weight or even more and to effect the weddingof the pigments, may conclude with co-micronizing thereof. Applicableratios of surface active agent material are subject to variationdepending on the particular organic and/or inorganic leuco pigmentmaterial being micronized and the particulate surface active agentmaterial employed, are not highly critical and may be optimizedempirically.

The composite chromoleuco pigment composition 8 with or without addedsurface active agent material 8a (which may be provided if thedispersion is to be stored for a substantial time before furtherprocessing) is then ready for the next step of the procedure.

When a nonaqueous micronizing liquid 3 is employed the present inventioncontemplates use as such liquid of a part or all of the ethylenicallyunsaturated monomer material to be employed in the polymerization step10 with or without added volatile organic solvent miscible with themonomer material and preferably removable prior to the polymerizationstep. In such instances the amount of surface active agent material 2employed in the micronizing step 5 can be reduced to zero or a part orall of the surface active agent or emulsifier to be used in the emulsionpolymerization may be present during the micronizing step or steps abovedescribed. Generally the same consideration as to proportions of liquidsto solids and empirical practices apply whether the micronizing liquid 3be aqueous or nonaqueous. Obviously, when micronizing in flammablematerial the temperature and the conditions of grinding, such asmaintenance of an inert atmosphere and the use of explosion-proofelectrical equipment must be controlled in the interests of safety. Whenit is desirable to employ a wash liquid 7 for removing fine pigmentdispersion from the micronizing medium, it is desirable to use a washingliquid which is employed as a component in the polymerization 10. Whensuch a nonaqueous micronizing system is employed the micronizedchromoleuco pigment composition from 6 is then emulsified in 8 with theaid of water 8b and surface active agent material 8a capable ofsupporting emulsion polymerization to form a pigment composition 8containing therein sufficient composite chromoleuco pigment material,surface active agent material, monomer material and water to form anemulsion polymerization composition which is charged to thepolymerization vessel 9. Should it be more convenient the necessarywater 8b and emulsifier material 8a, may be charged directly to thepolymerization vessel 9 and the nonaqueous pigment composition 8 addedthereafter. Preferably in either of the above procedures the degree ofmicronization is monitored during step 5 by microscopic examination ofsamples of the micronized slurry to determine when the necessary pigmentparticle size has been obtained, at which time the pigment composition 8is separated from the micronizing medium 6a e.g. sand, which may berecycled as at 5a to the micronizing apparatus employed to carry out themicronizing step 5.

During this micronizing step 5 there may also be incorporated ifdesired, additional adhesion or bonding agent components 1b, such aswater soluble alkali metal silicates, aminoplasts, phenoplasts, andtheir components, water soluble and/or dispersible polymer and the likeand/or nitrogenous materials, and/or monomer material should it bedesired to intimately admix the same during the micronizing step toensure formation of the composite chromoleuco pigment particles. Or, ifthis co-grinding is unnecessary said bonding agent material may beincorporated into the organic/inorganic pigment composition 8 asindicated by the dotted arrow.

In the next step the finely divided composite chromoleuco pigmententities in said composition 8 are converted intointrachromoleucospheruloid pigment by forming about them bodies ofessentially transparent polymer of not over 4 microns in particle sizediameter. To accomplish this step the composite chromoleuco pigmentcomposition 8 is charged to a polymerization vessel 9 with sufficientsurface active agent material 9a (additional to that supplied at 2and/or 8a), if necessary, to provide a total content of surface activeagent material appropriate for the emulsion polymerization of monomermaterial, e.g. 9b, with the aid of an emulsion polymerization initiator9d, which materials are also charged to the polymerization vessel.Sufficient monomer material is charged so that when polymerized to thedesired conversion, usually 100% conversion, the ratio of the compositechromoleuco pigment content to the polymer content of theintrachromoleucospheruloid pigment is in the range of 1:100 to 20:1(preferably 1:10 to 4:10). As indicated at 10a heat may be supplied toexpedite the polymerization 10, as is well known to those skilled in theemulsion polymerization art.

By such procedures the conversion step (b), produces from the micronizedcomposite chromoleuco pigment material and monomer material supplied, anessentially stable aqueous dispersion, i.e. latex, ofintrachromoleucospheruloid pigment composition 11, in which thecoloration of the organic color pigment and covering power of theinorganic leuco pigment, in combination in any vehicle of lesserrefractive index than the polymer of the spheruloids, aresynergistically enhanced by refraction and reflection within thespheruloids and at the interfaces between the spheruloids and vehicle.This latex form product may be utilized as such as in 11a for thecoloration of water based systems such as latex paints, printing inks,textile printing formulations, coloration of paper in the beater andsimilar fields of use, or may be further processed as shown in FIGS. 2through 6 to produce intrachromoleucospheruloid pigment in other forms.

As shown in FIG. 2 the intrachromoleucospheruloid pigment dispersion 11may be converted to a dry powdered product 11c by drying andpulverizing, preferably by spray drying, as shown at 11b. When spraydrying is employed the dispersion being dried may be reduced to a veryfine spray in order to obtain a finely divided spray dried productwithout additional processing.

Alternately the need for such a spray drying procedure may be reduced asshown in FIG. 3 by intimately mixing with the preferred cross-linkedinsoluble intrachromoleucospheruloid pigment dispersion 11, as at 12a,soft powdering additive(s) 12, with or without the aid of heat 12d, anddrying this mixture, which will produce the cross-linkedintrachromoleucospheruloid pigment in dried soft powder form 12c,requiring little or no mechanical attrition to constitute a usefulpowdered product. These dried intrachromoleucospheruloid pigmentproducts 11c and 12c are more readily shipped and stored than theintrachromoleucospheruloid pigment in latex or aqueously dispersed formand may be employed for the same purposes as above set forth inconnection with intrachromoleucospheruloid pigment latex 11a.

As shown in FIG. 4 instead of drying the intrachromoleucospheruloidpigment dispersion directly as in FIGS. 2 and 3, theintrachromoleucospheruloid pigment latex or dispersion may be coagulatedas at 13a with the aid of a coagulant 13, with or without the aid ofheat 13d, and the coagulum of intrachromoleucospheruloid pigment maythen be separated from the serum as at 13b e.g. by centrifuging orfiltering and washing, to produce the intrachromoleucospheruloid pigmentin wet presscake form 13c. Such wet presscake form has advantages forcertain uses where a product is required that is substantially free ofsurface active agent material and excess water; e.g. as in the flushedcolor industry, and may also be used for the same purposes as theintrachromoleucospheruloid pigment latex or dispersion 11a, or the driedintrachromoleucospheruloid pigment latex powders 11c and 12c havingsurface active agent material therein. The coagulatedintrachromoleucospheruloid pigment material 13a, which may have itscharacteristics modified by the coagulant and/or any other modifyingagent material which may be present therein, can itself be dried asindicated by the dotted arrow leading from 13a to 13e in FIG. 4, orwhere a dry intrachromoleucospheruloid pigment essentially free ofsurface active agent material and/or coagulant material residues ispreferred, the intrachromoleucospheruloid pigment presscake 13c may bedried as indicated by the dotted arrow leading from 13c to 13e forproducing such form of product 13f.

The procedure of FIG. 4 may be modified as shown in FIG. 5, by adding tothe intrachromoleucospheruloid pigment, latex or dispersion 11 whencross-linked to physical insolubility, not only coagulant material 13,but also soft powdering additive(s) 14, which may be introduced eitherbefore or after the coagulation is effected at 14a (with or without theaid of heat 14d). The so modified coagulated intrachromoleucospheruloidpigment dispersion may then be treated in the same manner as describedin connection with items 13b, 13c, 13e and 13f as indicated by therespectively corresponding items 14b, 14c, 14e and 14f in FIG. 5 and themodified products 14c and 14f include the soft powder advantagesdescribed in connection with FIG. 3.

Such dry insoluble intrachromoleucospheruloid pigments are especiallysuitable for incorporation into nonaqueous systems, especially oil basedpaint and printing inks and the opacifying and hue modification ofthermoplastic compounds.

For clarity in the following more detailed description andexemplification of the invention certain terms will be employed, themeaning of which we here set forth:

(1) ORGANIC COLOR PIGMENTS

The term "organic color pigments" as used herein designates the organicpigmentary materials which are colored as distinguished from water whiteor opaque white inorganic materials.

The invention may utilize any such organic color pigments and is notlimited to the use of any particular organic color pigment. Asillustrative but not restrictive of those that may be used to formintrachromoleucospheruloid pigments of this invention are those organiccolor pigments set out in the "Chemistry of Synthetic Dyes" by K.Venkataraman, Vol. V, especially Section 6, pages 314-474, AcademicPress, New York, N.Y., (1971), herein incorporated by reference, whichinclude pigments of the well known azo class exemplified by theacetoacetarylide azo, the pyrazolone azo, the α-naphthol azo, the2-hydroxy-3-naphthoic acid azo, the 2-hydroxy-3-naphtharylide azo andthe naphtholsulfonic acid azo pigments; the triphenylmethane pigmentsand related pigmentary compounds; the phthalocyanine pigments; theanthraquinone, indigoid and related pigments; the quinacridone pigments;the dioxazine pigments; the azamethine pigments; the fluororubinepigments; the naphthindolizinedione pigments; and other miscellaneousorganic pigmentary compositions; and those set out in "The Chemistry ofSynthetic Dyes and Pigments" by Herbert A. Lubs, Reinhold, New York(1955), herein incorporated by reference, and in "The Color Index", 3rdEdition (1973) published jointly by the "British Society of Dyers andColourists" and the "American Association of Textile Chemists andColorists", also herein incorporated by reference. Typicalrepresentatives of these organic color pigments are set forth in theexamples herein by way of illustration.

(2) INORGANIC PIGMENTS

The terms "inorganic pigments" and "inorganic pigment material" or"leucopigment material" as used herein designates the inorganicpigmentary materials both natural and manufactured in origin which areusually described as water white or "opaque white pigments". It alsoincludes for the purposes herein the semiopaque white pigments or"transparent white pigments" or "extender or filler pigments".

The invention may utilize any such inorganic pigments and is not limitedto the use of any particular inorganic pigment or pigments. Asillustrative but not restrictive of those that may be used to formintrachromoleucospheruloid pigments of this invention are the opaquewhite and transparent white pigments such as are referred to in theChemical Rubber Handbook 55th Edition 1974-1975; herein incorporated byreference; in the 3rd Edition (1973) of "The Color Index", Volume 3published jointly by the "British Society of Dyers and Colourists" andthe "American Association of Textile Chemists and Colorists", hereinincorporated by reference; and in Volume 1 of "The Pigment Handbook",published by John Wiley and Sons 1973, edited by Temple C. Patton, alsoherein incorporated by reference.

The most useful of the inorganic pigments for the purpose of thisinvention include, but are not limited to the siliceous pigmentsincluding the natural silica pigments, the precipitated silica pigments,the pyrogenic silica pigments, and alkaline-earth silicate pigments, thealuminum silicate pigments, the zinc silicate pigments, the zirconiumsilicate pigments; the titanium dioxide pigments and pigmentcompositions; alkaline-earth carbonate and sulfate pigments, the aluminaand hydrated aluminum oxide pigments, zirconium oxide pigments andcombinations of any two or more of such pigments. Typicalrepresentatives of these inorganic pigments are set forth in theexamples by way of illustration.

(3) SURFACE ACTIVE AGENT MATERIAL

Among the dispersing and/or emulsifying agents available for use assurface active agents herein we have found that the essential criterionfor such agent is that it, or it in combination with one or moreadditional dispersants and/or emulsifiers which may be used, should becapable of supporting emulsion polymerization. Having regard to thiscriterion surface active agents or as they are more generally classified"surfactants" (which encompasses both grinding, wetting and emulsifyingagents) may be either anionic, nonionic, cationic or amphoteric; ofeither singular molecular structure or polymeric nature; it beingunderstood that when two or more of such agents are employed togetherthey must be compatible with each other, except when minor proportionsof surfactants of opposite polarity are being used as wedding agent asabove described. Thus in the emulsion polymerization steps nonpolymericor polymeric anionic surfactants may be combined with each other and/orwith nonionic and/or amphoteric surfactants, polymeric or nonpolymeric;and nonpolymeric or polymeric cationic surfactants may be combined witheach other or with nonionic and/or amphoteric surfactants; andamphoteric and/or nonionic surfactants may be combined with each other.Thus it is possible to use a very wide range of commercially availablesurface active agents for achieving the degrees of grinding, theemulsion polymerization, and the production ofintrachromoleucospheruloid pigments as latices suitable for particularuses, as hereinafter exemplified, comprehensive listings of which areset out in the treatises "Detergents and Emulsifiers 1974 Annual" byJohn W. McCutcheon, published by John W. McCutcheon, Inc., Morristown,New Jersey, especially under the headings of Emulsifiers Suitable forEmulsion Polymerization, etc., and " Surface Active Agents andDetergents" by Anthony N. Schwartz et al, Interscience Publishers, Inc.,New York (1958), Vol. 2, pages 153-172, each of which is hereinincorporated by reference.

Among the commercially available surfactants may be mentioned theanionic surfactants, e.g. carboxylic acids and their derivatives,sulfonic esters, alkanesulfonates, alkylaryl sulfonates and phosphateesters; the effectively nonionic surfactants e.g. Alipal CO 433, thenonionic surfactants e.g. polyethenoxy ethers of alkylphenols,polyethenoxy ethers of alcohols and mercaptans, difunctional andpoly-functional polyethenoxy esters, miscellaneous polyethenoxy esters,polyethenoxy compounds with amide and miscellaneous linkages and variouspolyhydroxy compounds; the cationic surfactants, e.g. the straight chainalkyl ammonium compounds, the cyclic alkylammonium compounds, theolefin-derived compounds, and the quaternary compounds derived from thesame; the amphoteric surfactants e.g. those derived from betaines andphenolic solutions; and the polymeric surface active agents set out inthe said McCutcheon and Schwartz et al treatises. Typical examples ofrepresentative surfactants of these classes and combinations thereof areset forth in the Examples hereinafter, it being understood that saidExamples are but illustrative and not restrictive of the invention, e.g.the recently available fluorocarbon surfactants have also been foundeffective, especially when used in small proportions with other lessexpensive surfactants, for both the micronizing and the emulsionpolymerization steps. Typical of these fluorocarbon surfactants are the"Zonyl" trade-marked fluorocarbon surfactants of the DuPont Company,such as Zonyl A or P (anionic), Zonyl C (cationic), Zonyl N (nonionic),and Zonyl B (amphoteric).

(4) MICRONIZING

The term "micronizing" as used herein connotes the physical reduction inparticle size in a liquid medium of the organic and inorganic pigmentmaterials by means of an appropriate grinding system, e.g. a ball millor a sand mill, to the particle size desired in the step concerned, withthe aid of a surface active system if needed to assist the grinding andinhibit agglomeration of the micronized particles into aggregateparticles of larger size. Both ball mills and sand mills or sandgrinders are well known to the pigment art and commercially available.The balls in the case of ball mill, or the sand or like grindingmaterial in the case of the sand mill, are herein termed micronizingmedia.

(5) MONOMER MATERIALS

The monomer materials which may be used in practicing the presentinvention are the monomer compounds containing and emulsionpolymerizable through one or more ethylenically unsaturated >C ═C<groups to form homo-polymers, copolymers or grafted polymers toconstitute the essentially transparent particles formed about thecomposite pigment entities herein.

Such compounds containing and polymerizable through a single one of suchgroups produce linear polymers unless copolymerized with cross-linkingmonomer, i.e. monomer containing a plurality of such groups, whichcategory for the purpose of this invention, includes not only polyvinyl,polyalkyl and vinyl-allyl monomers but also the drying oil substancesemulsion copolymerizable with other ethylenically unsaturated compounds.

The polymer bodies surrounding the pigment particles in accordance withthis invention preferably are cross-linked to insolubility in allphysical solvents, but may be insoluble only in the intended environmentof use. With these criteria for guidance, the monomer materials andemulsion polymerization procedures employable may be selected by oneskilled in the art from any of those available. The fact ofcross-linking to insolubility in all physical solvents enhances theutility in that it also renders the cross-linked particles infusiblethus making the cross-linked material usable in any type ofthermoplastic material.

Among the mono-ethylenically unsaturated monomers available forpreparation of the improved pigment composition are mono-vinyl aromaticcompounds such as styrene, the methyl styrenes, the ethyl styrenes, thedimethyl styrenes, the diethyl styrenes, the isopropyl styrenes andmixed alkyl styrenes; nuclear substituted vinyl aryl alkyl, aralkyl,cycloalkyl, alkoxy, aryloxy, chloro, fluoro, chloromethyl, fluoromethyland trifluoromethyl nuclear derivatives; halogenated derivatives ofthese various aromatic vinyl compounds such as the mono and dichlorostyrenes; the alkyl substituted mono and dichloro styrenes; the vinylnaphthalenes, e.g. methyl vinyl naphthalene and their halogenatedderivatives; the vinyl aryl acids and vinyl alkyl acids such as acrylicacid and the alpha-alkyl substituted acrylic acids such as methacrylicacid, and esters of such acids as glycidyl, methyl, ethyl, propyl,butyl, isobutyl and other esters of aliphatic alcohols; the amides ofacrylic and methacrylic acid and derivatives thereof such as themethacrylamides, acrylamides, N-methylacrylamides,N-N-diethylacrylamide, N-ethylmethacrylamide,N-N-dimethylmethacrylamide, etc.; the nitriles such as acrylonitrile,methacrylonitrile, ethylacrylonitrile, chloroacrylonitrile and othernitriles; the alkyl esters of alphaethylenic aliphatic dicarboxylicacids such as diethyl fumarate and diethyl-chloro maleate; theunsaturated ketones, methyl vinyl ketone and methyl isopropenyl ketone;the vinyl pyridines; the vinyl quinolines; vinyl furans; vinylcarbazoles, the esters of vinyl alcohols such as vinyl acetate;acetylamino substituted acrylic and methacrylic acids, and their esters,methyl, ethyl, propyl- and the like such as α-acetaminoacrylate and theα-n-butyraminoacrylates, etc.; the ethers of olefinic alocholsespecially the ethers of vinyl and allyl type alcohols such as vinylethyl ether, vinyl butyl ether, vinyl tolyl ether, divinyl ether, methylisopropenyl ether, methallyl ethyl ether; the unsaturated aldehydes suchas acrolein and methacrolein and the like; the allyl and vinyl nitrogenring compounds such as triallylcyanurate; copolymerizable alkenylchlorides including methallyl chloride, allyl chloride, vinyltrichloride, vinylidene chloride, 1-chloro-1-fluoro ethylene and4-chlorobutene-1; and the vinylidines.

Among the cross-linking or polyethylenically unsaturated monomers whichmay be used alone or in combination with other emulsion polymerizableethylenically unsaturated compounds, are the polyvinyl, polyallyl andvinylallyl compounds such as polyvinyl aromatic compounds, for exampledivinylbenzene, divinyltoluene, divinylxyline, divinylethylbenzene,trivinylbenzene, divinylnaphthalene, divinylmethylnaphthalenes; thevinyl esters, allyl esters and vinyl allyl esters of carboxylic andpolycarboxylic acids including polymerizable ester monomers such asdiallyl maleate, vinylcrotonate, allyl methacrylate, allyl acrylate,ethylene glycol dimethacrylate, divinylsuccinate, divinyladipate,vinylacrylate, vinylmethacrylate.

The copolymerizable "drying oils" which may be used as cross-linkingagents include the poly-unsaturated fish oils which oils are capable offorming films by oxidation on exposure to air and further include theseoils in their raw state, in bodied form and/or otherwise modified, as byair blowing. The term "drying oil substances" includes (1) the dryingoils, especially those containing conjugated unsaturation e.g., tungoil, oiticica oil, isano oil, conjugated linseed oil, conjugated soyabean oils, fish oil, etc., (2) the air blown or bodied drying oils,whether from conjugated or nonconjugated drying oils and whether bodiedby heat and/or catalytically, (3) the fatty acids including theirdimers, trimers and tetramers derived from such drying or modifieddrying oils.

In preparing modified improved intrachromoleucospheruloid pigmentcompositions by graft polymerization techniques, active sites may beprovided on the spheruloids by grafting with butadiene, isoprene,piperyline, methyl pentadiene and/or other hydrocarbon dienes and alsothe polar dienes such as chloroprene and cyanobutadiene.

(6) POLYMERIZATION INITIATOR

Examples of suitable emulsion polymerization catalysts or initiatorsthat may be used include water soluble catalysts such as the perborates,persulfates and perchlorates of potassium sodium and ammonia; which maybe used with or without small amounts of heavy metal salts such as thoseof iron, cobalt, etc.; with or without a reducing agent such as sodiumbisulfite or metabisulfite, or the catalyst may be an inorganic peroxidesuch as barium peroxide, sodium peroxide, hydrogen peroxide; andaliphatic acyl peroxide such as acetyl peroxide, lauryl peroxide,stearyl peroxide; an aromatic acyl peroxide such as benzoyl peroxide, orphthaloyl peroxide; a mixed peroxide such as acetyl benzoyl peroxide,acetyl stearyl peroxide; organic aliphatic and aromatic azo compoundssuch as azobisisobutyronitrile and certain azo dye structures; or it maybe a hydroperoxide such as cumene hydroperoxide or diisopropylbenzenehydroperoxide which is often used with a reducing agent such astetraethylene pentamine, and ferrous sulfate as a source of iron withsodium or potassium pyrophosphate to complex the iron.

Heat or radiation may also serve to initiate or facilitate emulsionpolymerization.

A mercaptan such as dodecylmercaptan may sometimes be used in smallamounts as a polymerization initiator, whereas in larger amounts itserves as a polymerization modifier; or aluminum salts such as thehalides; organic and inorganic acids; metal compounds of the unsaturatedacids such as cobalt and manganese resinates, linoleates and maleatesmay be used. The catalyst system chosen is only important insofar as itaffects the rate of the polymerization reaction, always taking intoaccount that the system chosen must not react unfavorably with thepigment or pigments being used.

(7) PH ADJUSTMENT

By pH adjustment is meant the addition of either acid or base to adjustthe pH for micronizing and/or polymerization to within the desiredranges for the purpose in question, e.g. for efficiency and/orcompatibility with the pigmentary, monomeric, and/or surfactantmaterials being used. Preferred additives are the organic acids such asacetic, formic, or hydroxyacetic to lower the pH, and ammonium hydroxideto raise the pH. Inorganic acids and/or bases may be used provided theydo not form objectionable amounts of salts which would interfere withthe process or attack the equipment being used.

(8) POLYMERIZATION VESSEL

By polymerization vessel is meant any suitable vessel equipped with thenecessary mechanical stirrer, temperature controls, and apertures foraddition of reactants prior and during the polymerization step,constructed of suitable materials such as stainless steel or preferablyglass lined to avoid contamination of the polymerization ingredients.

(9) EMULSION POLYMERIZATION

By the term emulsion polymerization is meant the polymerization inaqueous medium of polymerizable ethylenically unsaturated monomer ormonomers, linear or cross-linking in nature, in such a manner that thepolymer formed is a latex.

(10) CHROMOLEUCO OR CHROMOLEUCO COMPOSITE

The term "chromoleuco" or "chromoleuco composite" as used hereinconnotes the composite particles from the two components thereof,organic color pigment material and inorganic leuco pigment materialwedded together. This wedding may be effected by co-micronizing theparticles so that freshly fractured areas of one component, with theelectrical charges associated therewith, are brought into intimatecontact with the freshly fractured areas of the other component, wherebythe particles of the respective components are wedded to each other.Such wedding may also be effected by separately micronizing the organicand inorganic components in aqueous media with the aid of predominantlynonionic or weakly anionic surface active agents such as, e.g. TritonX405 and Alipal CO 433, containing respectively a small proportion, inthe range of 1-10% by weight of the total surface active agent, of ionicsurface active agents of opposite polarity, preferably cationic in thecase of the inorganic pigment, and then combining and co-micronizing theso formed dispersions, whereby the anionically and cationically preparedpigment particles are intimately attracted to each other and becomewedded in the liquid medium to form composite particles which remaindispersed in the liquid medium with the aid of the nonionic emulsifierwhich is employed in sufficient amount to maintain such compositedispersion when formed. The wedding of the organic color pigment to theinorganic leuco pigment to form the composite pigment particles, may beaided when necessary or desired, depending on the particular pigmentsemployed, by the co-grinding with the combined components of 0 to anequal weight based on the inorganic pigment, of suitable bonding agentand/or nitrogenous material selected from the classes hereinafter setforth.

(11) INTRACHROMOLEUCOSPHERULOID PIGMENT

The term "intrachromoleucospheruloid pigment" as used herein designatesspheruloids of essentially transparent polymer material, preferablycross-linked to essential insolubility in all physical solvents, and ofan average particle size of not more than 4 microns, having embeddedtherein still smaller particles of organic color pigment and inorganicpigment material. The transparent spheruloids of preferably cross-linkedpolymer, in any medium of lesser refractive index in which they areinsoluble, preserve the attained particle size of the embedded pigmentmaterial and enhance the hue and apparent strength and opacity of thesame, thus providing a new and useful color pigment composition.

(12) LATEX

By the term latex is meant the aqueous dispersion' of theintrachromoleucospheruloid pigment composition in which theintrachromoleucospheruloid pigment particles are so small that they areessentially non-settling.

(13) SOFT POWDERING AGENT(S)

The term soft powdering agent(s) or additive(s) as used herein connotesmaterials selected from the class consisting of aliphatic,cycloaliphatic and aromatic hydrocarbons and their alcohols havingboiling points between 90° C. and 200° C. preferably the predominantlyaliphatic hydrocarbon solvents of this class such as solvent naphtha,and Stoddard solvent. Naphtha solvent, or solvent naphtha, is a mixtureof low boiling hydrocarbons having a boiling point range of 90-165° C.obtained in the distillation of coal tar, petroleum or shale oil, andmay contain appreciable portions of benzene or its homologues. Stoddardsolvent is a petroleum distillate with minimum flash point of 100° F.,90% distillable at 375° F. with an end point of 410° F.

In accordance with this invention, said hydrocarbon materials arepreferably applied in conjunction with an oil-soluble surface activeagent. The oil-soluble surface active agent is selected from that classof materials extensively defined by Schwartz, Perry and Berch in theirbook Surface Active Agents and Detergents, Vol. II, IntersciencePublishers, Inc., New York (1958), especially at pages 244-247 and pages597-605, herein incorporated by reference. So useful surface activeagents include the dialkyl sulfosuccinates, the mahogany sulfonates,long chain (16-18 carbon atoms) alkyl aromatic sulfonates, dialkylnaphthalene sulfonic acids, esters of higher fatty acids, higher aminesalts of naphthalene sulfonic acids, lanolin, lanolin fatty acids,naphthenic acids and their salts, glycol ethers, acyclic alcohols andketo alcohols, fatty alkylol amides and the sorbitan and polyethenoxysorbitan nonionics.

(14) SOFT POWDER PRODUCTS

The term "soft powder" or "soft powdered" intrachromoleucospheruloidpigment as applied to products producable by the present inventionconnotes the physical characteristic resulting from the treatment hereindisclosed of the aqueously wet, never previously dried, cross-linkedinsoluble intrachromoleucospheruloid pigment with the aforesaid softpowdering agents before drying the same to a dry pigment product, i.e.the characteristic that the soft powdered dried product has such a softform that it is in, or readily reduced to, a fine soft powder withoutany extended attrition, thereby being more readily dispersible in anymedium than the same product not so treated. The mechanism accountingfor this characteristic is not clearly understood, but it is believedthat the hydrocarbon components of the soft powdering additives, whichare carried onto the surfaces of the intrachromoleucospheruloid pigmentparticles by means of the oil soluble surfactant components thereofwhich may be wholly or partially removed by washing, inhibit hydrogenbridging between the intrachromoleucospheruloid pigment particles byoccupying the sites at which such could occur until after theelimination from the system of the aqueous phase, said hydrocarboncomposite being thereafter substantially removable at a more elevatedtemperature when their presence is not desired in the soft powderedproduct.

(15) COAGULANT

By coagulant we mean any additive capable of destabilizing theemulsified system under consideration, for causing coagulation of itssolids content; the coagulant used will of course vary depending largelyon the type of system, i.e. the type of surfactant used and/or thefunctionality, if any, of the intrachromoleucospheruloid polymers. Forexample, anionic systems may be coagulated with either acids such asacetic or formic, hydrochloric, sulfuric, alkaline-earth metal salts,zinc and aluminum and other colorless ions of heavy metals, watersoluble alcohols, or water insoluble amines preferably as their watersoluble salts. Cationic systems may be coagulated with water insolubleacids, preferably as the water soluble alkali metal salts thereof and/orthe water soluble amines thereof, and ammonium hydroxide or watersoluble alcohols. Nonionic systems are often coagulated with watersoluble alcohols with or without the addition of acids. Anionic laticesof intrachromoleucospheruloid pigment may also be coagulated bycombining therewith cationic latices of intrachromoleucospheruloidpigment material surfaced with cationic surfactants and vice versa.

(16) PIGMENT MODIFYING, WEDDING AND BONDING AGENTS

The organic and/or inorganic pigment components, the composites formedtherefrom, and/or the intrachromoleucospheruloid pigment materialsproduced by the process may be modified either physically or chemicallyby the addition or incorporation of modifying or bonding material duringor subsequent to the micronizing step. For example such material may bea bonding agent to aid in bonding the previously wedded compositeorganic/inorganic pigment particles in the polymer spheruloids; or tosubsequently aid the fixation of the intrachromoleucospheruloid pigmentproduct to a substrate material. The modifying agent may comprise one ormore of those substances or compounds which may be employed, althoughnot essential to the process, to obtain certain specific advantages ormodifications to the process or products thereof. Such substances mayinclude nitrogenous material such as water soluble or insoluble amines,imines and polyamines and polyimines, added to the inorganic pigmentmaterial during the micronizing step to render it more oleophilic, i.e.more substantive to the organic pigment material and the organic polymermaterial, and/or water soluble or dispersible condensation resinproducts aminoplasts or phenoplasts or the components thereof, addedduring the micronizing or subsequent steps for the same purpose. Byreactants which form aminoplastics or aminoplasts we mean urea,melamine, thiourea and guanidine, etc., condensed with formaldehyde,glyoxal, etc. By reactants to form phenoplasts we mean phenol and/orsubstituted phenolic alcohols such as the resols, xylenols and/orresorcinol, etc., condensable with formaldehyde and/or higher aldehydessuch as glyoxal or furfural, etc. We use the term phenolplasts in thesame manner as used by T. S. Carswell in his book entitled "Phenoplasts.Their Structure, Properties and Chemical Technology," published in 1947by Interscience Publishers, Inc., New York, N. Y. We use the termaminoplastics in the same manner that C. P. Vale uses this term in hisbook entitled, "Aminoplastics," published in 1950 by Cleaver-Hume Press,Ltd., London, England.

Pigment bonding agents which may be used to aid fixation of thecomponents of the composite chromoleuco pigment to each other and toorganic polymer material, may be inorganic, e.g. a water soluble alkalimetal silicate or a water soluble titanium composed for example,titanium tetrachloride or oxychloride, precipitated in situ on at leastthe inorganic component.

A bonding agent may also be ethylenically unsaturated monomer materialto be absorbed and/or absorbed by the wedded pigment material during themicronizing step, and then be polymerized subsequently with the aid of apolymerization initiator.

The water soluble organo-silane compounds, e.g. Z6020 Silane availablefrom Dow Chemical Company may be used to increase the affinity of theorganic to the inorganic components especially in effecting the weddingof the pigment components.

Bonding agents which may be used to aid the substantivity of theinorganic to the organic phase of the intrachromoleucospheruloidpigments also include aqueous solutions or dispersions of organicpolymers depositable on the inorganic pigment material and containingcarboxy, amine, sulfate, and/or sulfonic acid groups, salts thereof,nitrogenous containing material such as oleophilic amines, oleophilicimines, oleophilic amine carboxylates, oleophilic quaternary ammoniumcompounds, water soluble polyamines, water soluble imines andcombinations thereof as aforementioned.

(17) SEPARATION BY SCREENING

Separation by screening, or conventional screening where employed in theExamples herein, connotes that the micronized composite pigment materialis washed away from the micronizing medium and the screen with dilutingliquid or a part thereof.

(18) 50% DIVINYLBENZENE

The term 50% divinylbenzene as used herein denotes the commerciallyavailable product regarded as an approximately equal mixture of divinyland mono-vinyl materials.

(19) MICROSCOPIC EXAMINATION

The term microscopic examination as used in the Examples hereinafterdenotes examination with an optical microscope, i.e. a Leitz "Ortholux"research microscope, which is regarded as having a resolving power of0.2 micron and a lower limit of visibility for well separated particlesof 0.02 micron diameter, and average particle sizes herein set forthwere determined accordingly.

In the examples given hereinafter, a particular point of distinctionbetween the preferred cross-linked embodiments of the invention and theless preferred noncross-linked embodiments is that the cross-linkingrenders the spheruloids not only insoluble in physical solvents, butalso nonfusible. Thus the preferred embodiments are particularly adaptedfor coloring plastic melts before extrusion, as the infusibility assuresintegrity of the spheruloids under extrusion temperatures and insuresagainst any alteration of the flow characteristics of the melt, whichmay be caused by softening of the spheruloids in the case of the lesspreferred embodiments. In addition, the cross-linking of a polymerincreases its density and thus increases its refractive index to adegree. Therefore the cross-linking, as well as the choice of monomermaterials used, aids in adapting the product to have the necessarydifference in refractive index from that of a vehicle in which it isintended to be used, particularly when the vehicle has a density orrefractive index only slightly below that of the correspondingnoncross-linked spheruloids.

Whether the spheruloids are cross-linked or noncross-linked, theiruniformity in size and spheruloidal nature particularly adapt them foruse in electrostatic coating systems, and by controlling thepolymerization conditions as above exemplified the size of thespheruloids may be maintained within specified limits adapting them forglass or matte finishes or for special purposes as desired.

In the Examples herein set forth the product from the polymerizationstep was determined by microscopic examination to be in spheruloids ofless than 4.0 microns average diameter, and was essentially nonsettlingi.e. a latex.

Further more, materials designated herein by chemical name under "TradeName" are of commercial grade; those designated by proprietary namethereunder are further identified therewith.

By way of being illustrative of the scope of this invention but not tobe interpreted as being restrictive in any manner, the followingExamples are given in both detailed procedural and table form:

Examples 1-5; Detailed step-wise procedures for producing cross-linkedinsoluble intrachromoleucospheruloid pigment compositions.

Tables 1-10 Preparation of intrachromoleucospheruloid pigment materialusing cross-linked polymer material.

Tables 11-20 Preparation of intrachromoleucospheruloid pigment materialusing noncross-linked polymer material.

Examples A et seq. Additional detailed step-wise procedures forproducing intrachromoleucospheruloid pigment compositions in variousforms.

EXAMPLES 1-5 Detailed step-wise Procedures for Producing Cross-linkedInsoluble Intrachromoleucospheruloid Pigment Composition EXAMPLE 1(Preparation as a dry product)

To a sand mill is charged 30 grams of Perylene Red Toner (Pigment Red123, CI 71145), 10 grams of Irgazin Yellow 3 RLT (Pigment Yellow 110),30 grams of Titanium Dioxide pigment (TiPure LW, DuPont), 20 grams of28% "N" Sodium Silicate (28% aqueous solution), 2 grams of Tamol SN(sodium salt of condensed naphthalene sulfonic acid), 100 grams of 20%aqueous solution of a styrene/methacrylic acid/acrylonitrile copolymer(ratio 25/65/10, NH₄ OH salt), 10 grams of 28% NH₄ OH, 300 ml. of waterand 300 volumetric parts of Ottawa sand. The charge is milled in air forsome 48 hours until a representative sample under microscopicexamination shows essentially all of the pigment present to be below 0.2micron in diameter and to be essentially free of unwedded components.The charge is separated from the micronizing medium by conventionalscreening and the pigment dispersion diluted to 600 ml. volume withwater and placed in a vessel equipped for emulsion polymerization; 80grams of a monomer mixture consisting of 30 grams styrene, 30 grams ofmethylmethacrylate and 20 grams of 50% divinylbenzene are added and thetemperature raised to 40° C. 3 grams of cumene hydroperoxide are addedat this point and the polymerization mixture heated to 70-75° C. andheld at this temperature for 7 hours.

The bright orange latex is allowed to cool and diluted with an equalvolume of water. The aqueous dispersion so formed is then caused tocoagulate by the addition of 50 ml. of glacial acetic acid as a 20%aqueous solution. The slurry is then heated to 70° C. and filtered,washed and dried in an oven. On micropulverizing the dried presscakematerial, a brillant orange red intrachromoleucospheruloid pigment isobtained which may be utilized in the coloration of oil based paints,inks and thermoplastic materials.

EXAMPLE 2 (Preparation as a wet presscake pigment for flushing into oilbased systems)

The procedure of Example 1 is followed with the exception that theproduct following filtration is retained as a wet presscake, suitablefor the coloration of aqueous based systems such as paper pulp, latexpaints; and also for flushing into oil based vehicles.

EXAMPLE 3 (Preparation as a latex)

40 grams of Heliogen Blue BG (dry basis) in the form of a wet 35%presscake is charged to a sand grinding apparatus together with 10 gramsof Titanium Dioxide pigment (TiPure R900 DuPont), 40 grams ofreinforcing grade dry silica pigment HiSil 233, PPG), 10 grams ofdimethylaminoethylmethacrylate, 2 grams of Duponol ME (sodium laurylsulfate), 5 grams of a 10% aqueous solution of tetraethylenepentamine,20 grams of Triton X405 (octylphenoxy polyethoxy ethanol), 10 ml. of 28%NH₄ OH, 300 ml. of water and 300 volumetric parts of Ottawa said. Thecharge is milled until a representative sample under microscopicexamination shows essentially all of the pigment material therein to bebelow 0.2 micron in diameter and no separate unwedded components to bevisible. The pigment dispersion is separated from the micronizing mediumby conventional screening and charged to a vessel equipped for emulsionpolymerization containing therein 50 grams of Triton X405 (octylphenoxypolyethoxy ethanol) and the volume adjusted to 700 ml. with water. Amonomer mixture consisting of 50 grams of methyl methacrylate and 10grams of ethyleneglycoldimethacrylate is added and the temperatureraised to 40-45° C. of 3 grams of cumene hydroperoxide are added and theheating continued to 70-75° C. The polymerization reaction is held atthis temperature range for 7 hours. On cooling a bright strong blueintrachromoleucospheruloid pigment latex is obtained. Microscopicexamination reveals this to consist of spheruloids of organic polymermaterial having embedded therein the composite chromoleuco pigmentcomposition reflecting the augmented brightness of the leuco pigmentcomponents and the augmented color of the chromo components, with novisible separation of said component pigment material, said spheruloidsbeing essentially below 0.5 micron in diameter.

EXAMPLE 4 (Preparation of Intrachromoleucospheruloid pigment in variousforms)

The intrachromoleucospheruloid latex product in the preceding Example isdischarged to a vessel equipped with stirrer, temperature controls andbaffles for producing turbulent agitation and diluted to 2000 ml. volumewith water. 20 grams of a water soluble polyethylenimine (PEI 600manufactured by Dow) are added, followed by 40 ml. of glacial aceticacid to effect coagulation. The slurry is stirred for 10 minutes andthen 40 ml. of a 10% solution of sorbitan monolaurate dissolved inSolvent Naphtha add. The slurry is then heated to 75-80° C. and held atthis temperature range for 4-5 hours. A portion of this slurry is thenfiltered and washed to produce a bright blue intrachromoleucospheruloidpigment in presscake form having polyethylenimine present therein andthus having increased affinity for cellulosic material.

A portion of the slurry is spray dried to give theintrachromoleucospheruloid pigment in spray dried powder form, withsimilar utility to that of the presscake material, and having the addedadvantages of storage stability and reduced handling weight.

A portion of the filtered and washed presscake material is redispersedin sufficient water to provide a 20% solids slurry and then spray driedto give a bright blue soft powdered intrachromoleucospheruloid pigmentin spray dried soft powder form essentially free of water solublesurface active agent material and salts. This product is extremelysuitable for the coloration of oil based vehicles, inks andthermoplastics.

A portion of the filtered and washed presscake material is oven dried toproduce the intrachromoleucospheruloid pigment in soft powder form,requiring little or no further mechanical grinding to be suitable forany of the above given uses.

EXAMPLE 5 (Micronizing of the dry pigment materials with monomers)

A mixture of 20 grams of Heliogen Green A, (Pigment Green 7, CI 74260),30 grams of Irgazin Yellow 3RLT (Pigment Yellow 110) 4 grams ofMonazoline T (substituted imidazoline of Tall Oil), 20 grams of HiSil233, a precipitated dry silica pigment, 10 grams of Titanium Dioxidepigment, 100 grams of styrene, and 40 grams ofdimethylaminoethylmethacrylate are micronized in a sand grindingapparatus equipped with explosion proof electrical fittings, coolingapparatus and nitrogen blanket together with 200 volumetric parts ofOttawa sand until a representative sample under microscopic examinationshows that all of the pigment material is essentially below 0.2 micronin diameter and essentially free of unwedded components. 20 grams of 50%divinylbenzene is added and the micronizing continued for 2 hours. Thethus prepared composite pigment dispersion in monomer material is thenseparated from the grinding medium by screening and charged with rapidstirring to a vessel equipped for emulsion polymerization containingtherein an aqueous solution of 35 grams of N-tallow trimethylene diaminediacetate in 400 grams of water. The emulsion polymerization mixture soformed is then heated to 45° C. at which point 200 grams of an aqueoussolution containing 3 grams of potassium persulfate and 1.25 grams ofsodium bisulfite are added. The reaction temperature is raised to 60-65°C. and held at this range for 7 hours.

On cooling a bright green intrachromoleucospheruloid latex is obtained;a representative sample under microscopic examination shows essentiallyall of the spheruloids thereof to be below 0.5 micron in diameter and tobe uniformly colored with no evidence of separation of the organic andinorganic components from the polymer spheruloids. The latex is used asis, for coloration of aqueous based systems; or may be further processedas shown in the preceding examples to yield theintrachromoleucospheruloid pigment in its various wet and dry forms.

The following tabular Examples further exemplify the application of theprocedures hereinabove set forth, give the proportions of ingredients ingrams, in the order of their addition and the order of the processingoperations, as well as the nature of the products produced thereby.

TABLES 1-10

Preparation of Intrachromoleucospheruloid Pigment Material usingCross-linked Polymer Material.

                                      TABLE 1                                     __________________________________________________________________________    Prepartion of Intrachromoleucospheruloid Pigment Composition                  (parts by weight)                                                             Example No. 1-     1    2     3     4      5                                  __________________________________________________________________________    A. Micronizing Step                                                           1. Organic Color Pigment                                                         Class           Phthalo-                                                                           Vat   Azo   Quinacridone                                                                         Azo                                                   cyanine                                                       Trade Name      Heliogen                                                                           Ponsol                                                                              Permanent                                                                           Magenta                                                                              Permagen                                              Blue BG                                                                            Jade Green                                                                          Carmine      Yellow                                Color Index Name                                                                              Blue 15                                                                            Green 1                                                                             Red 5 Red 122                                                                              Yellow 14                             Color Index Number                                                                            74160                                                                              59825 12490 --     21095                                 Pigment, dry basis                                                                            1*   10    20    25     50                                 2. Inorganic Pigment                                                             Trade Name      HiSil 233                                                                          Hisil 404                                                                           Cab-O-Sil                                                                           --     Cab-O-Sil                                                        H-5          H5                                    Pigment, dry basis                                                                            90   30    50    --     0.25                               3. Inorganic Pigment                                                             Trade Name      TiPure                                                                             TiPure LW                                                                           --    TiPure R941                                                                          TiPure LW                                             R900             Slurry                                       Pigment, dry basis                                                                            9    40    --    50     0.25                               4. Surface Active Agent**                                                        Material (Trade Name)                                                         Alipal CO 433.sup.1                                                                           9    40    25    25     25.                                   Tamol SN.sup.2  1    --    --    --     2                                     Monazoline T.sup.3                                                                            1    1     --    --     1                                     Ammonium Hydroxide 28%                                                                        10   --    --    5      10                                    Acetic Acid     --   5     5     --     --                                 5. Water, quantity 500  300   400   395    300                                6. Micronizing Step                                                              Method          Sand Sand  Sand  Ball   Ball                                  Time, Hours, approx.                                                                          48   32    24    48     32                                    Temperature, ° C.                                                                      28   28    28    28     28                                    Average Particle Size                                                         Diameter (microns)                                                            of Composite    <0.2 <0.2  <0.2  <0.2   <0.2                                  Pigment                                                                    7. Separation, Screening (X)                                                                     X    X     X     X      X                                  8. Water, dilution 1000 300   300   200    211.5                              9. Yield - Aqueous Pigment                                                       Composition (dispersion)                                                                      1621 686   800   700    600                                B. Polymerization Step                                                        10.                                                                              Surface Active Agent**                                                        (a) Quantity, type                                                                            130.sup.1                                                                          --    25.sup.1                                                                            9.sup.1                                                                              --                                    (b) Quantity, type                                                                            --   --    1.sup.3                                                                             1.sup.3                                                                              --                                    Water           50   --    24    --     --                                    Acetic Acid     --   --    --    --     --                                    Ammonium Hydroxide 28%                                                                        20   --    --    10     5                                  11a.                                                                             Monomer Material                                                              Non Crosslinking                                                              Styrene         800  6     38    40     --                                    Dimethylaminoethylmethacrylate                                                                --   --    2     --     --                                    Methylmethacrylate                                                                            --   --    40    --     50                                    4-vinylpyridine --   --    --    10     --                                 11b                                                                              Monomer Material                                                              Crosslinking                                                                  Divinylbenzene 50%                                                                            200  2     20    10     --                                    Ethyleneglycoldimethacrylate                                                                  --   --    --    --     10                                    Polymerization Initiator                                                      AZDN.sup.4      20   1     --    3      2                                     Potassium Persulfate                                                                          --   --    3     --     --                                    Sodium Bisulfite                                                                              --   --    1.5   --     --                                    Polymerization Conditions                                                     Time, hours, approx.                                                                          10   4     5     6      5                                     Temperature, ° C.                                                                      80   80    70    75     80                                    Conversion, approx. 100% (X)                                                                  X    X     X     X      X                                     Intrachromoleucospheruloid                                                    Pigment Dispersion                                                            Yield           2821 694   950   580    667                                   Average Particle Size                                                         Diameter (microns)                                                                            <4.0 <4.0  <4.0  <4.0   <4.0                               __________________________________________________________________________     *used as wet presscake material                                               **capable of effecting polymerization                                         .sup.1 sodium salt of a sulfate ester of an alkylphenoxy                      poly(ethyleneoxy)ethanol (28% active)                                         .sup.2 sodium salt of a condensed napthalene sulfonic acid                    .sup.3 substituted imidazoline of tall oil (100% active)                      .sup.4 azobisisobutyronitrile                                                 TiPure tradename for DuPont titanium dioxide pigment                          HiSil tradename for PPG Industries precipitated silica                        Cab-O-Sil tradename for Cabot Corporation pyrogenic silica               

                                      TABLE 2                                     __________________________________________________________________________    Preparation of Intrachromoleucospheruloid Pigment Composition                 (parts by weight)                                                             Example No. 2-     1      2     3     4      5                                __________________________________________________________________________    A. Micronizing Step                                                           1. Organic Color Pigment                                                         Class           Dioxazine                                                                            Azamethine                                                                          Phthalo-                                                                            Vat    Misc.                                                            cyanine                                          Trade Name      Heliogen                                                                             Irgazin                                                                             Heliogen                                                                            Indanthrene                                                                          Aniline                                             Violet R                                                                             Yellow 2                                                                            Green A                                                                             Pink R Black                                               Toner  GLT                                                    Color Index Name                                                                              Violet 23                                                                            Yellow 109                                                                          Green 7                                                                             Red 1  Black 1                             Color Index Number                                                                            51319  --    74260 73360  50440                               Pigment, dry basis                                                                            20     30    25*   30*    30                               2. Inorganic Pigment                                                             Trade Name      TiPure R941                                                                          --    --    --     --                                                  Slurry                                                        Pigment, dry basis                                                                            30     --    --    --     --                               3. Inorganic Pigment                                                             Trade Name      HiSil 404                                                                            Cab-O-Sil                                                                           Micro-Cel                                                                           A-Sil-Ate                                                                            Santocel                                                   M5    T38   W      62                                  Pigment, dry basis                                                                            30     40    50    40     45                               4. Surface Active Agent**                                                        Material (Trade Name)                                                         Triton X405.sup.1                                                                             80     --    --    40     30                                  Triton X400.sup.2                                                                             --     25    --    --     --                                  Duomeen T.sup.3 --     --    20    --     --                                  Monaquat TIBO.sup.4                                                                           --     --    --    1      1                                   Ammonium Hydroxide 28%                                                                        10     --    --    --     --                                  Acetic Acid     --     10    10    5      2                                5. Water, quantity 330    395   395   384    392                              6. Micronizing                                                                   Method          Ball   Sand  Sand  Ball   Sand                                Time, hours, approx.                                                                          48     48    36    60     36                                  Temperature, ° C.                                                                      28     28    28    28     28                                  Average Particle Size                                                         Diameter (microns)                                                            of Composite    <0.2   <0.2  <0.1  <0.1   <0.1                                Pigment                                                                    7. Separation, Screening (X)                                                                     X      X     X     X      X                                8. Water, dilutions                                                                              200    200   200   300    300                              9. Yield, Aqueous Pigment                                                        Composition (dispersion)                                                                      700    700   700   800    800                              B. Polymerization Step                                                        10.                                                                              Surface Active Agent**                                                        (a) Quantity, type                                                                            200.sup.1                                                                            20.sup.1                                                                            --    20.sup.1                                                                             3.sup.4                             (b) Quantity, type                                                                            --     --    --    --     --                                  Water           --     75    --    70     5                                   Ammonium Hydroxide 28%                                                                        20     --    --    10     --                                  Acetic Acid     --     5     --    --     2                                11a                                                                              Monomer Material                                                              Non Crosslinking                                                              Styrene         18     80    40    80     20                                  Cyclohexylmethacrylate                                                                        --     10    40    --     60                                  Dimethylaminoethyl-                                                           methacrylate    --     --    10    2      10                               11b.                                                                             Monomer Material                                                              Crosslinking                                                                  Divinylbenzene 50%                                                                            2      10    --    18     --                                  Ethyleneglycoldimeth-                                                         acrylate        --     --    10    --     10                                  Polymerization Initiator                                                      AZDN.sup.5      --     3     --    3      3                                   Cumene Hydroperoxide                                                                          2      --    3     --     --                                  Polymerization Conditions                                                     Time, hours, approx.                                                                          4      5     6     6      5                                   Temperature, °C.                                                                       80     80    75    80     80                                  Conversion, approx. 100% (X)                                                                  X      X     X     X      X                                   Intrachromoleucospheruloid                                                    Pigment Dispersion                                                            Yield           900    900   800   1000   910                                 Average Particle Size                                                         Diameter (microns)                                                                            <4.0   <4.0  <4.0  <4.0   <4.0                             __________________________________________________________________________     Example 2-2-a This example is prepared exactly as in Example 2-2 except       that the 10 parts of 50% divinylbenzene are added subsequent to the           initial polymerization in step 13 and polymerized sequentially in the         Intrachromoleucospheruloid pigment composition (14) with the aid of 1/2       part of azobisisobutyrnitrile to yield a cross-linked                         Intrachromoleucospheruloid pigment composition.                               Example 2-4-a This example is prepared exactly as in example 2-4 except       that the 18 parts of 50% divinylbenzene are added subsequent to the           initial polymerization in step 13 together with 12 parts of                   cyclohexylmethacrylate and 1 part of azobisisobutyronitrile and               polymerized sequentially in the Intrachromoleucospheruloid pigment            composition (14) to yield 1012 parts of cross-linked                          Intrachromoleucospheruloid pigment composition.                               *used as wet presscake material                                               **capable of effecting emulsion polymerization                                .sup.1 octylphenoxy polyethoxy ethanol (70% active)?                          .sup.2 stearyl dimethyl benzyl ammonium chloride (82% active)                 .sup.3 N-tallow trimethylene diamine (85% active)                             .sup.4 substituted imidazoline quaternized with benzyl chloride (100%         active)                                                                       .sup.5 azobisisobutyronitrile.                                                TiPure tradename for DuPont titanium dioxide pigment                          HiSil tradename for PPG Industries precipitated silica                        Cab-O-Sil tradename for Johns-Mansville calcium silicate                      Micro-cel tradename for Johns-Mansville calcium silicate                      A-Sil-Ate tradename for Freeport Kaolin Company aluminum silicate             Santocel tradename for Monsanto Corporation aerogel silica               

                                      TABLE 3                                     __________________________________________________________________________    Preparation of Intrachromoleucospheruloid Pigment Composition                 (parts by weight)                                                             Example No. 3      1      2      3      4    5                                __________________________________________________________________________    A. Micronizing Step                                                           1. Organic Color Pigment                                                         Class           Vat    Azamethine                                                                           Quinacridone                                                                         Phthalo-                                                                           Azo                                                                      cyanine                                  Trade Name      Indanthrene                                                                          Iragazin                                                                             Monastral                                                                            Polymon                                                                            Permanent                                           Brilliant                                                                            Red 2 BLT                                                                            Red Y  Blue G                                                                             Carmine                                             Orange RK                                                     Color Index Name                                                                              Orange 7                                                                             Red 180                                                                              Violet 19                                                                            Blue 16                                                                            Red 5                               Color Index Number                                                                            71105  --     46500  74100                                                                              12490                               Pigment, dry basis                                                                            40*    30     25     30   35                               2. Inorganic Pigment                                                             Trade Name or type                                                                            HiSil 404                                                                            TiPure Unitane                                                                              Titanox                                                                            Horse-                                                                        head                                                       R941 Slurry                                                                          OR 450 RA47 R771                                Pigment, dry basis                                                                            20     32     30     40   50                               3. Inorganic Pigment                                                             Trade Name or type                                                                            HiSil 233                                                                            HiSil 233                                                                            Cab-O-Sil M5                                                                         HiSil 233                                                                          HiSil 233                           Pigment, dry basis                                                                            30     40     20     30   30                               4. Surface Active Agent**                                                        Material (Trade Name)                                                         Alipal CO 433.sup.1                                                                           20     10     --     --   --                                  Triton X405.sup.2                                                                             --     50     20     --   10                                  Duomeen T.sup.3 --     --     --     25   30                                  Monazoline T.sup.4                                                                            --     1      1      --   --                                  Zonyl FSA.sup.5 1      --     --     --   --                                  Zonyl FSC.sup.6 --     --     --     1    --                                  Ammonium Hydroxide 28%                                                                        10     10     5      --   --                                  Acetic Acid     --     --     --     12   15                               5. Water, quantity 479    327    399    362  330                              6. Micronizing                                                                   Method          Ball   Sand   Sand   Ball Ball                                Time, hours, approx.                                                                          36     48     48     60   60                                  Temperature, ° C.                                                                      28     28     28     28   28                                  Average Particle Size                                                         Diameter (microns)                                                            of Composite    <0.05  <0.1   <0.2   <0.02                                                                              <0.2                                Pigment                                                                    7. Separation, Screening (X)                                                                     X      X      X      X    X                                8. Water, dilution 300    300    300    200  200                              9. Yield - Aqueous Pigment                                                       Composition (dispersion)                                                                      900    800    800    700  700                              B. Polymerization Step                                                        10.                                                                              Surface Active Agent**                                                        (a) Quantity, type                                                                            20.sup.2                                                                             20.sup.1                                                                             20.sup. 1                                                                            25.sup.3                                                                           25.sup.2                            (b) Quantity, type                                                                            --     --     20.sup.2                                                                             --   --                                  Water           25     70     50     63   20                                  Ammonium Hydroxide 28%                                                                        5      10     10     --   --                                  Acetic Acid     --     --     --     12   5                                11a.                                                                             Monomer Material                                                              Non Crosslinking                                                              Styrene         30     --     --     40   60                                  Methylmethacrylate                                                                            40     50     --     40   50                                  Diethylaminoethylmethacrylate                                                                 5      10     5      5    5                                   Cyclohexylmethacrylate                                                                        --     20     --     --   15                               11b.                                                                             Monomer Material                                                              Crosslinking                                                                  Divinylbenzene 50%                                                                            10     --     --     --   20                                  Allylacrylate   5      10     --     5    --                                  Ethyleneglycoldimethacrylate                                                                  --     10     95     10   --                                  Polymerization Initiator                                                      AZDN.sup.7      3      4      5      2    5                                   Cumene Hydroperoxide                                                                          1      --     --     2    --                                  Polymerization Conditions                                                     Time, hours, approx.                                                                          6      8      8      5    7                                   Temperature, °C.                                                                       80     75     80     80   80                                  Conversion, approx. 100% (X)                                                                  X      X      X      X    X                                   Intrachromoleucospheruloid                                                    Pigment Dispersion                                                            Yield           1040   1000   1000   900  900                                 Average Particle Size                                                         Diameter (microns)                                                                            <4.0   <4.0   <4.0   <4.0 < 4.0                            __________________________________________________________________________     *used as wet presscake material                                               **capable of effecting emulsion                                               .sup.1 sodium salt of a sulfate ester of an                                   alkylphenoxypoly(ethyleneoxy)ethanol (28%                                     .sup.2 octylphenoxy polyethoxy ethanol (70%                                   .sup.3 N-tallow trimethylene diamine (85%                                     .sup.4 substituted imidazoline of tall oil (100%                              .sup.5 fluorochemical surface active agent (50%                               .sup.6 fluorochemical surface active agent (50%                               .sup.7 azobisisobutyronitrile                                                 TiPure tradename for DuPont titanium dioxide pigment                          Unitane tradename for American Cyanamid Company titanium dioxide pigment      Titanox tradname for National Lead Industries titanium dioxide pigment        Horsehead tradename for New Jersey Zinc Company titanium dioxide pigment      HiSil tradename for PPG Industries precipitated silica                        Cab-O-Sil tradename for Cabot Corporation pyrogenic silica               

                                      TABLE 4                                     __________________________________________________________________________    Preparation of Intrachromoleucospheruloid Pigment Composition                 (parts by weight)                                                             Example No. 4-     1      2     3      4     5                                __________________________________________________________________________    A. Micronizing Step                                                           1. Organic Color Pigment                                                         Class           Phthalo-                                                                             Vat   Cond. Azo                                                                            Dioxazine                                                                           Vat                                                 cyanine                                                       Tradename       Green  Amanthren                                                                           Chromoptal                                                                           Heliogen                                                                            Indanthren                                          Y.E.X. Black BNN                                                                           Red BR Violet                                                                              Blue BC                             Color Index Name                                                                              Green 41                                                                             Green 9                                                                             --     Violet 23                                                                           Blue 6                              Color Index Number                                                                            --     59850 --     51319 69825                               Pigment, dry basis                                                                            20     40    30     20*   40*                              2. Inorganic Pigment                                                             Trade Name or type                                                                            Tronex Unitane                                                                             Unitane                                                                              TiPure                                                                              Barium                                              CR800  OR520 CR640  R960  Sulfate                                                                       Pigment                                                                       White 5                             Pigment, dry basis                                                                            30     20    40     30    20                               3. Inorganic Pigment                                                             Trade Name or Type                                                                            Zinc   Cab-O-Sil                                                                           HiSil 233                                                                            HiSil                                                     Oxide  M5           404   TiPure R941                                         (Pig. White 4)            Slurry                              Pigment, dry basis                                                                            15     20    30     20    32                               4. Surface Active Agent**                                                        Material (Trade Name)                                                         Alipal CO433.sup.1                                                                            18     --    --     --    10                                  Triton X405.sup.2                                                                             30     10    20     --    25                                  Duomac T.sup.3  --     20    --     30    --                                  Monaquat TIBC.sup.4                                                                           2      --    20     --    2                                   Zonyl FSB.sup.5 --     --    1      1     --                                  Tamol SN.sup.6  2      --    --     --    --                                  Ammonium Hydroixde 28%                                                                        10     --    --     --    10                                  Acetic Acid     --     10    10     15    --                               5. Water, quantity 373    280   299    384   361                              6. Micronizing                                                                   Method          Sand   Ball  Ball   Ball  Sand                                Time, hours, approx.                                                                          24     36    60     48    48                                  Temperature, ° C.                                                                      28     28    28     28    28                                  Average Particle Size                                                         Diameter (microns)                                                            of Composite    <0.1   <0.05 <0.2   <0.2  <0.1                                Pigment                                                                    7. Separation, Screening (X)                                                                     X      X     X      X     X                                8. Water, dilution 200    200   250    200   250                              9. Yield Aqueous Pigment                                                         Composition (dispersion)                                                                      700    600   700    700   750                              B. Polymerization Step                                                        10.                                                                              Surface Acitive Agent**                                                       (a) Quantity, type                                                                            30.sup.2                                                                             20.sup.2                                                                            40.sup.2                                                                             20.sup.2                                                                            100.sup.1                           (b) Quantity, type                                                                            --     10.sup.3                                                                            10.sup.4                                                                             --    --                                  Water           60     65    45     --    --                                  Ammonium Hydroxide 28%                                                                        10     --    --     --    10                                  Acetic Acid     --     5     5      --    --                               11a.                                                                             Monomer Material                                                              Non Crosslinking                                                              Styrene         80     60    40     --    --                                  Vinyltoluene    10     --    --     40    --                                  Methylmethacrylate                                                                            --     40    30     20    --                                  Dimethylaminoethylmethacrylate                                                                2      2     --     5     --                               11b.                                                                             Monomer Material                                                              Crosslinking                                                                  Divinylbenzene 50%                                                                            --     18    --     --    --                                  Ethyleneglycoldimethacrylate                                                                  8      --    10     5     90                                  Polymerization Initiator                                                      Potassium Persulfate                                                                          3      --    3      --    --                                  Sodium Bisulfite                                                                              1.5    --    1.5    --    --                                  AZDN.sup.7      --     3     --     3     4                                   Polymerization Conditions                                                     Time, hours, approx.                                                                          7      7     6      5     6                                   Temperature, ° C.                                                                      60     75    65     75    80                                  Conversion, approx 100% (X)                                                                   X      X     X      X     X                                   Intrachromoleucospheruloid                                                    Pigment Dispersion                                                            Yield           900    820   880    800   900                                 Average Particle Size                                                         Diameter (microns)                                                                            <4.0   <4.0  <4.0   <4.0  <4.0                             __________________________________________________________________________     Example 4-1-a. This example is prepared exactly as in Example 4-1 except      that the 30 parts of titanium dioxide, Tronex CR800 are replaced by 30        parts of a natural silica pigment, Min-U-Sil (produced by PGS).               Example 4-2-a. This example is prepared exactly as in Example 4-2 except      that the 20 parts of Cab-O-Sil N5 are replaced by 20 parts of zirconium       silicate, "Excelopax" (manufactured by NL Tam. Div.)                          Example 4-2-b. This example is prepared exactly as in Example 4-2 except      that the 20 parts of Unitane OR520 are replaced by 20 parts of zirconium      oxide, pigment white 12. (Manufactured by NL Tam. Div.)                       Example 4-2-c. This example is prepared exactly as in Example 4-2 except      that the 20 parts of Cab-O-Sil M5 are replaced by 20 parts of alumina         hydrate (manufactured by Alcoa).                                              Example 4-5-a. This example is prepared exactly as in Example 4-5 except      that the 20 parts of Barium Sulfate Pigment White 5 are replaced by 20        parts of Celite 110, a natural silica pigment (manufactured by                Johns-Manville Company).                                                      Example 4-5-b. This example is prepared exactly as in Example 4-5 except      that the 20 parts of Barium Sulfate Pigment White 5 are replaced by 20        parts of Pigment White 20, aluminum Potassium Silicate.                       *used as wet presscake material                                               **capable of effecting emulsion polymerization                                .sup.1 sodium salt of a sulfate ester of an alkylphenoxy                      poly(ethyleneoxy)ethanol (28% active)                                         .sup.2 octylphenoxy polyethoxy ethanol (70% active)                           .sup.3 N-tallow trimethylene diamine diacetate (85% active)                   .sup.4 substituted imidazoline quaternized with benzyl chloride (100%         active)                                                                       .sup.5 fluorochemical surface active agent (50% active)                       .sup.6 sodium slat of a condensed napthalene sulfonic acid                    .sup.7 azobisisobutyronitrile                                                 Tonex tradename for Kerr-McGee Company titanium dioxide pigment               Unitane tradename for American Cyanamid Company titanium dioxide pigment      TiPure tradename for DuPont titanium dioxide pigment                          Cab-O-Sil tradename for Cabot Corporation pyrogenic silica                    HiSil tradename for PPG Industries precipatated silica                   

                                      TABLE 5                                     __________________________________________________________________________    Preparation of Intrachromoleucospheruloid Pigment Composition                 (parts by weight)                                                             Example No. 5-     1    2    3     4      5                                   __________________________________________________________________________    A. Micronizing Step                                                           1. Organic Color Pigment                                                         Class           Phthalo-                                                                           Phthalo-                                                                           Vat   Vat    Azamethine                                             cyanine                                                                            cyanine                                                  Trade Name      Heliogen                                                                           Heliogen                                                                           Ponsol                                                                              Indanthrene                                                                          Irgazin                                                Blue BG                                                                            Green A                                                                            Jade Green                                                                          Red FBBA                                                                             Red 2BLT                               Color Index Name                                                                              Blue 15                                                                            Green 7                                                                            Green 1                                                                             Red 10 Red 180                                Color Index Number                                                                            74160                                                                              74260                                                                              59825 67000  --                                     Pigment, dry basis                                                                            25*  30   30*   35     25                                  2. Inorganic Pigment                                                             Trade Name or Type                                                                            Titanox                                                                            Unitane                                                                            TiPure                                                                              TiPure Titanox                                                RA   0220 R941  R900   RA                                     Pigment, dry basis                                                                            30   40   40    50     30                                  3. Inorganic Pigment                                                             Trade Name or Type                                                                            HiSil 233                                                                          HiSil 404                                                                          Cab-O-Sil                                                                           Ludox Coll-                                                                          Barcid                                                           M-5   oidal Silica                                                                         Macaloid                               Pigment, dry basis                                                                            20   30   40    40     10                                  4. Surface Active Agent**                                                        Material, Trade Name                                                          Triton X305.sup.1                                                                             20   --   10    --     --                                     Triton X400.sup.2                                                                             --   20   --    20     --                                     Triton X405.sup.3                                                                             20   20   30    --     20                                     Tamol SN.sup.4  2    --   1     --     --                                     Duomeen T.sup.5 2    --   1     20     1                                      Ammonium Hydroxide 28%                                                                        --   --   --    --     --                                     Acetic Acid     --   5    5     10     5                                   5. Water, quantity 331  355  343   325    309                                 6. Micronizing                                                                   Method          Sand Sand Sand  Ball   Sand                                   Time, hours, approx.                                                                          36   24   36    72     48                                     Temperature, °C.                                                                       28   28   28    28     28                                     Average Particle Size                                                         Diameter (microns)                                                            of Composite    <0.02                                                                              <0.2 <0.1  <0.02  <0.1                                   Pigment                                                                    7. Separation, Sceening (X)                                                                      X    X    X     X      X                                   8. Water, dilution 250  200  200   200    200                                 9. Yeild, Aqueous Pigment                                                        Composition (dispersion)                                                                      700  700  700   700    600                                 B. Polymerization Step                                                        10.                                                                              Surface Active Agent**                                                        (a) Quantity-type                                                                             --   20.sup.3                                                                           --    20.sup.5                                                                             40.sup.3                               (b) Quantity-type                                                                             --   --   --    --     --                                     Water           --   20   --    70     35                                     Ammonium Hydroxide 28%                                                                        10   --   --    --     25                                     Acetic Acid     --   10   --    10     --                                  11a.                                                                             Monomer Material                                                              Non Crosslinking                                                              Vinyltoluene    75   70   70    60     78                                     4-Vinylpyridine 5    5    10    10.5   --                                     Methacrylic Acid                                                                              --   --   --    8.5    --                                     Methylmethacrylate                                                                            --   --   --    10     20                                     Dimethylaminoethylmethacrylate                                                                --   --   --    1      12                                  11b.                                                                             Monomer Material                                                              Crosslinking                                                                  Divinylbenzene 50%                                                                            9.5  15   20    --     --                                     Oiticica Oil    0.5  --   --    --     10                                     Ethyleneglycoldimethacrylate                                                                  --   --   --    10     --                                     Polymerization Initiator                                                      AZDN.sup.6      3    --   3     4      4                                      Cumene Hydroperoxide                                                                          --   3    --    --     --                                     Polymerization Conditions                                                     Time, hours, approx.                                                                          6    5    5     6      7                                      Temperature, °C.                                                                       90   80   80    75     90                                     Conversion, approx. 100% (X)                                                                  X    X    X     X      X                                      Intrachromoleucospheruloid                                                    Pigment Dispersion                                                            Yield           800  840  800   900    800                                    Average Particle Size                                                         Diameter (microns)                                                                            <4.0 <4.0 <4.0  <4.0   <4.0                                __________________________________________________________________________     Example 5-1-a. This example is prepared exactly as Example 5-1 except tha     the 30 parts of titanium dioxide are replaced by 20 parts of magnesium        oxide.                                                                        Example 5-1-b. This example is prepared exactly as Example 5-1 except tha     the 30 parts of titanium dioxide are replaced by 30 parts of alumina.         Example 5-1-c. This example is prepared exactly as in example 5-1 except      that the 20 parts of silica (HiSil 233) are replaced by 20 parts of           hydrated aluminum oxide.                                                      Example 5-3-a. This example is prepared exactly as in Example 5-3 except      that the 40 parts of titanium dioxide are replaced by 40 parts of antimon     oxide.                                                                        Example 5-3-b. This example is prepared exactly as in Example 5-3 except      that the 40 parts of titanium dioxide are replaced with 40 parts of zinc      oxide.                                                                        Example 5-5-a. This example is prepared exactly as in Example 5-5 except      that the 40 parts of titanium dioxide are replaced with 40 parts of           zirconium oxide.                                                              *used as wet presscake material                                               **capable of effecting emulsion polymerization                                .sup.1 octylphenoxy polyethoxy ethanol (70% active)                           .sup.2 stearyl dimethyl benzyl ammonium chloride (82% active)                 .sup.3 octylphenoxy polyethoxy ethanol (70% active)                           .sup.4 sodium salt of a condensed napthalene sulfonic acid                    .sup.5 N-tallow trimethylene diamine (85% active)                             .sup.6 azobisisobutyronitrile                                                 Titanox tradename for National Lead Industries titanium dioxide pigment       Unitane tradename for American Cyanamid Company titanium dioxide pigment      TiPure tradename for DuPont titanium dioxide pigment                          HiSil tradename for PPG Industries precipitated silica                        Cab-O-Sil tradename for Cabot Corporation pyrogenic silica                    Ludox tradename for DuPont colloidal silica                                   Baroid Macaloid tradename for NL Industries magnesium silicate           

                                      TABLE 6                                     __________________________________________________________________________    Preparation of Intrachromoleucospheruloid Pigment Composition                 (parts by weight)                                                             Example No. 6-     1      2     3    4     5                                  __________________________________________________________________________    A. Micronizing Step                                                           1. Organic Color Pigment                                                         Class           Phthalo-                                                                             Dioxazine                                                                           Vat  Triphenyl                                                                           Vat                                                   cyanine           methane                                     Trade Name      Heliogen                                                                             Carbazole                                                                           Perylene                                                                           Victoria                                                                            Brilliant                                             Blue BG                                                                              Violet                                                                              Red  Blue  Orange RK                             Color Index Name                                                                              Blue 15                                                                              Violet 23                                                                           Red 29                                                                             Blue 1                                                                              Orange 3                              Color Index Number                                                                            74160  51319 71140                                                                              42595 59300                                 Pigment, dry basis                                                                            25*    20*   30   15    30                                 2. Inorganic Pigment                                                             Trade Name or Type                                                                            TiPure TiPure LW                                                                           Titanox                                                                            Unitase                                                                             TiPure                                                R941 Slurry  RA 45                                                                              OR 560                                                                              LW                                    Pigment, dry basis                                                                            40     20    40   30    30                                 3. Inorganic Pigment                                                             Trade Name or Type                                                                            HiSil 233                                                                            Excelopax                                                                           Oncor                                                                              HiSil EP                                                                            Silene D                                                     Zirconium                                                                           23A                                                                     Silicate                                               Pigment, dry basis                                                                            30     30    20   30    20                                 4. Surface Active Agent                                                          Material (Trade Name)                                                         Triton X405.sup.1                                                                             10     5     20   30    --                                    Alipal C0433.sup.2                                                                            72     5     --   --    20                                    Tamol 731.sup.3 --     5     --   --    --                                    Monazoline T.sup.4                                                                            1      1     20   --    2                                     SAMV Amph. Copolymer.sup.5                                                                    --     --    20   --    20                                    N-group polymer.sup.6                                                                         --     10    --   20    --                                    SMA Copolymer.sup.7                                                                           20     --    --   --    --                                    Sulfobetaine DC 50%.sup.8                                                                     --     --    10   --    --                                    Ammonium Hydroxide 28%                                                                        10     5     --   --    10                                    Acetic Acid     --     --    5    5     --                                 5. Water, quantity 292    299   235  270   268                                6. Micronizing Step                                                              Method          Ball   Sand  Sand Ball  Sand                                  Time, hours, approx.                                                                          36     48    48   60    32                                    Temperature, ° C.                                                                      28     28    28   28    28                                    Average Particle Size                                                         Diameter (microns)                                                            of Composite    <0.2   <0.2  <0.2 <0.2  <0.2                                  Pigment                                                                    7. Separation, Screening (X)                                                                     X      X     X    X     X                                  8. Water, dilution 200    300   300  200   300                                9. Yield, Aqueous Pigment                                                        Composition (dispersion)                                                                      700    700   700  600   700                                B. Polymerization Step                                                        10.                                                                              Surface Active Agent                                                          (a) Quantity, type                                                                            --     25.sup.1                                                                            20.sup.1                                                                           20.sup.1                                                                            20.sup.1                              (b) Quantity, type                                                                            --     10.sup.6                                                                            10.sup.2                                                                           20.sup.2                                                                            20.sup.8                              Water           --     55    70   60    55                                    Ammonium Hydroxide 28%                                                                        --     10    --   --    5                                     Acetic Acid     --     --    --   --    --                                 11a.                                                                             Monomer Material                                                              Non Crosslinking                                                              Styrene         80     60    --   20    --                                    Methylmethacrylate                                                                            --     10    20   --    43                                    Cyclohexylmethacrylate                                                                        --     10    10   20    --                                    Diethylaminoethylemthacrylate                                                                 --     --    --   --    2                                  11b.                                                                             Monomer Material                                                              Crosslinking                                                                  Divinylbenzene 50%                                                                            20     10    --   10    --                                    Allylacrylate   --     10    --   --    --                                    Ethyleneglycoldimethacrylate                                                                  --     --    4.5  --    5                                     Tung Oil        --     --    0.5  --    --                                    Polymerization Initiator                                                      AZDN.sup.9      3      4     --   2     2                                     Cumene Hydroperoxide                                                                          --     --    3    --    --                                    Polymerization Conditions                                                     Time, hours, approx.                                                                          5      6     5    4     4                                     Temperature, ° C.                                                                      80     75    85   80    80                                    approx. 100% (X)                                                                              X      X     X    X     X                                     Intrachromoleucospheruloid                                                    Pigment Dispersion                                                            Yield           800    900   835  750   850                                   Average Particle Size                                                         Diameter (microns)                                                                            <4.0   <4.0  <4.0 <4.0  <4.0                               __________________________________________________________________________     *used as wet presscake material                                               **capable of effecting emulsion polymerization                                .sup.1 octylphenoxy polyethoxy ethanol (70% active)                           .sup.2 sodium salt of sulfate ester of an alkylphenoxy                        poly(ethyleneoxy)ethanol (28% active)                                         .sup.3 sodium salt of a polycarboxylic acid (100% active)                     .sup.4 substituted imidazoline of tall oil                                    .sup.5 copolymer of styrene, acrylonitrile, methacrylic acid and              4-vinylpyridine, ratio 25/10/29/36                                            .sup.6 4-vinylpyridine homopolymer                                            .sup.7 Copolymer of styrene, methacrylic acid and acrylonitrile, ratio        25/65/10                                                                      .sup.8 stripped coco ammonium sulfonic acid betaine (50% active)              .sup.9 azobisisobutyronitrile                                                 TiPure tradename for DuPont titanium dioxide pigment                          Titanox tradename for National Lead Industries titanium dioxide pigment       Unitane tradename for American Cyanamid titanium dioxide pigment              HiSil tradename for PPG precipitated silica                                   Excelopax tradename for National Lead Industries zirconium silicates          Uncor tradename for National Lead Industries antimony oxide/silica pigmen     Silene tradename for PPG precipitated silica                             

                                      TABLE 7                                     __________________________________________________________________________    Preparation of Intrachromoleucospheruloid Pigment Composition                 (Parts by weight)                                                             Example No. 7-       1     2     3      4     5                               __________________________________________________________________________    A. Micronizing Step                                                           1. Organic Color Pigement                                                        Class             Vat   Azo   Quinacridone                                                                         Phthalo-                                                                            Dioxazine                                                               cyanine                                  Trade Name        Ponsol                                                                              Permagen                                                                            Magneta                                                                              Polymon                                                                             Irgazin                                              Jade Green                                                                          Yellow       Blue G                                                                              Violet 6RLT                        Color Index Name  Green 1                                                                             Yellow 14                                                                           Red 122                                                                              Blue 16                                                                             --                                 Color Index Number                                                                              59825 21095 --     74100 --                                 Pigment, dry basis                                                                              20*   40    20*    30    20                              2. Inorganic Pigment                                                             Trade Name        HiSil 233                                                                           Excelopax                                                                           Micro-cel                                                                            Cab-O-Sil                                                                           HiSiN 404                                                  Zirconium                                                                           T-38   M-5                                                              Silicate                                              Pigment, dry basis                                                                              30    30    10     30    30                              3. Inorganic Pigment                                                             Trade Name        TiPure LW                                                                           Oncor 23A                                                                           Aluminum                                                                             TiPure                                                                              TiPure LW                                                        Oxide  R941                                     Pigment, dry basis                                                                              20    30    20     40    40                              4. Surface Active Agent**                                                        Material, Trade Name                                                          Alipal CO 433.sup.1                                                                             20    --    --     10    --                                 Monazoline T.sup.2                                                                              2     --    --     --    2                                  Zonyl FSH.sup.3   1     --    --     --    --                                 Duomeen T.sup.4   --    20    --     2     20                                 Monaquat TIBO.sup.5                                                                             --    10    10     --    10                                 Triton X405.sup.6 --    --    5      20    --                                 Ammonium Hydroxide                                                                              --    --    --     10    --                                 Acetic Acid       --    10    --     --    10                              5. Water, quantity   298   260   235    258   368                             6. Micronizing Step                                                              Method            Sand  Sand  Sand   Sand  Ball                               Time, hour, approx.                                                                             36    48    36     48    60                                 Temperature, ° C.                                                                        28    28    28     28    28                                 Average Particle Size                                                         Diameter (microns)                                                            of Composite      <0.1  <0.2  <0.2   0.1-0.2                                                                             <0.1                               Pigment                                                                    7. Separation, Screening (X)                                                                       X     X     X      X     X                               8. Water, dilution   200   200   200    300   300                             9. Yield Aqueous Pigment                                                         Composition (dispersion)                                                                        600   600   500    700   800                             B. Polymerizatio Step                                                         10.                                                                              Surface Active Agent**                                                        (a) Quantity, type                                                                              --    --    --     25.sup.6                                                                            --                                 (b) Quantity, type                                                                              --    --    --     --    --                                 Water             95    --    --     75    --                                 Acetic Acid       --    --    --     --    --                                 Ammonium Hydroxide 28%                                                                          5     --    --     --    --                              11a.                                                                             Monomer Material                                                              Non Crosslinking                                                              Styrene           48    --    60     40    80                                 Methylmethacrylate                                                                              10    40    --     20    --                                 Dimethylaminoethylmethacrylate                                                                  2     2     2      --    --                                 4-vinylpyridine   --    --    --     5     --                              11b.                                                                             Monomer Material                                                              Crosslinking                                                                  Ethyleneglycoldimethacrylate                                                                    5     3     --     --    --                                 Allylacrylate     5     --    --     --    --                                 Divinylbenzene 50 %                                                                             --    --    8      15    20                                 Polymerization Initiator                                                      AZDN.sup.7        2     2     3      1     --                                 Potassium Persulfate                                                                            --    --    --     --    3                                  Sodium Bisulfite  --    --    --     --    1.5                                Cumene Hydroperoxide                                                                            --    --    --     2     --                                 Polymerization Conditions                                                     Time, hours, approx.                                                                            5     5     6      7     6                                  Temperature, °  C.                                                                       80    80    75     75    80                                 Conversion, approx. 100% (X)                                                                    X     X     X      X     X                                  Intrachromoleucospheruloid                                                    Pigment Dispersion - Yield                                                                      770   645   570    780   900                                Average particle Size                                                         Diameter (microns)                                                                              <4.0  <4.0  <4.0   <4.0  <4.0 - 15. Water, Dilution,                                                   approx. 3000 3000 2500 3000                                                   3500                               Soft Powdering Additive                                                       Type              --    --    20.sup.1                                                                             10.sup.b                                                                            10.sup.a                           Coagulant Additive                                                                              .sup.c                                                                              .sup.d                                                                              .sup.e .sup.f                                                                              .sup.g                          Temperature, ° C. approx.                                                 30                30    30    30     30                                       Reaction Temperature, ° C.                                                               80    80    80     80    80                                 Reaction Time, hours, approx.                                                                   6     6     7      7     6                               20.                                                                              Isolation Method                                                              Filtration and washing (X)                                                                      X     --    X      X     --                                 Product Available as wet coagulum                                                               X     --    X      X     --                                 (X)               22.   Drying Method                                         Oven              X     --    X      X     --                                 Spray             --    X     --     --    X                                  Dry Intrachromoleucospheruloid                                                Pigment - Yield (approx.)                                                                       140   175   130    180   220                                Soft Powder Form (X)                                                                            --    --    X      X     X                                Example 7-4-a This example is prepared exactly as Example 7-4 except that     the 20 parts of soft powdering additive type .sup.a are replaced by 40        parts of solvent naphtha with 10 parts of a dioctyl ester of sodium           sulfosuccinic acid dissolved therein.                                         Example 7-4-b This example is prepared exactly as Example 7-4 except that     the 20 parts of soft powdering additive type .sup.1 are replaced by 5         parts of dioctylphthalate dissolved in 30 parts of Solvesso 140.              *used as wet presscake material                                               **capable of effecting emulsion polymerization                                .sup.1 sodium salt of a sulfate ester of an alkylphenoxy                      poly(ethyleneoxy)ethanol (28% active)                                         .sup.2 substituted imidazoline of tall oil (100% active)                      .sup.3 fluorochemical surface active agent (100% active)                      .sup.4 N-tallow trimethylene diamine (85% active)                             .sup.5 substituted imidazoline quaternized with benzyl chloride (100%         active)                                                                       .sup.6 octylphenoxy polyethoxy ethanol (70% active)                           .sup.7 azobisisobutyronitrile                                                 HiSil tradename for PPG Industreis precipitated silica                        Excelopax tradename for National Lead Industries zirconium silicate           Micro-Cel tradename for Johns-Manville calcium silicate                       Cab-O-Sil tradename for Cabot Corporation pyrogenic silica                    TiPure tradename for DuPont titanium dioxide pigment                          Oncor tradename for National Lead Industries antimony oxide/silica pigmen     .sup.a 20% solution of diamyl sodium sulfosuccinate in Solvesso 140           .sup.b 20% solution of di-tertiary-octyl sodium sulfosuccinate in Solvent     Naphtha                                                                       .sup.c acetic acid                                                            .sup.d NH.sub.4 OH                                                            .sup.e acetic acid                                                            .sup.f aqueous H.sub.2 SO.sub.4                                               .sup.g NH.sub.4 OH                                                       

                                      TABLE 8                                     __________________________________________________________________________    Preparation of Intrachromoleucospheruloid Pigment Composition                 (parts by weight)                                                             Example No. 8-     1             2                                            __________________________________________________________________________    A. Micronizing Step                                                           1. Organic Color Pigment                                                         Class           Phthalocyanine                                                                        Azo   Vat   Triphenyl-                                                                    methane                                   Trade Name      Heliogen                                                                              Permagen                                                                            Indanthren                                                                          Victoria                                                  Blue BG Yellow                                                                              Blue BC                                                                             Blue                                      Color Index Name                                                                              Blue 15 Yellow 14                                                                           Blue 6                                                                              Blue 1                                    Color Index Number                                                                            74160   21095 69825 42595                                     Pigment, dry basis                                                                            5*      45    25*   5                                      2. Inorganic Pigment                                                             Trade Name or Type                                                                            HiSil 233    HiSil 233                                        Pigment, dry basis                                                                            30           25                                            3. Inorganic Pigment                                                             Trade Name or Type                                                                            TiPure LW    TiPure R941 Slurry                               Pigment, dry basis                                                                            30           30                                            4. Surface Active Agent                                                          Material (Trade Name)                                                         Alipal CO433.sup.1                                                                            --           10                                               Triton X405.sup.2                                                                             20           10                                               Duomeen T.sup.3 20           --                                               Tamol SN.sup.4  --           2                                                Ammonium hydroxide 28%                                                                        --           10                                               Acetic Acid     10           --                                            5. Water, quantity 340          383                                           6. Micronizing Step                                                              Method          Ball         Sand                                             Time, hours, approx.                                                                          60           48                                               Temperature, 9°C.                                                                      28           28                                               Average Particle Size                                                         Diameter (microns)                                                            of Composite    <0.2         0.2-0.1                                          Pigment                                                                    7. Separation, Screening (X)                                                                     X            X                                             8. Water, dilution 200          200                                           9. Yield Aqueous Pigment                                                         Composition (dispersion)                                                                      700          700                                           B. Polymerization Step                                                        10.                                                                              Surface Active Agent                                                          (a) Quantity, type                                                                            20.sup.2     40.sup.1                                         (b) Quantity, type                                                                            10.sup.3     --                                               Water           65           50                                               Ammonium hydroxide 28%                                                                        --           10                                               Acetic Acid     5            --                                            11a.                                                                             Monomer Material                                                              Non Crosslinking                                                              Methylmethacrylate                                                                            40           50                                               Cyclohexylmethacrylate                                                                        10           --                                            11b.                                                                             Monomer Material                                                              Crosslinking                                                                  Ethyleneglycoldimethacrylate                                                                  10           10                                               Polymerization Initiator                                                      AZDN            --           3                                                Cumene Hydroperoxide                                                                          3            --                                               Polymerization Conditions                                                     Time, hours, approx.                                                                          7            6                                                Temperature, °C.                                                                       75           80                                               Conversion, approx. 100% (X)                                                                  X            X                                                Intrachromoleucospheruloid                                                    Pigment Dispersion                                                            Yield           860          860                                           __________________________________________________________________________     Example 8-1-a. This example is prepared exactly as Example 8-1 except tha     the 5 parts of Pigment Blue 15 are replaced by 20 parts of Pigment Green      and the 45 parts of Pigment Yellow 14 are replaced by 30 parts of Pigment     Yellow 110.                                                                   Example 8-2-a. This example is prepared exactly as Example 8-2 except tha     the 25 parts of Vat Blue 6 are replaced by 25 parts of Pigment Violet 19      and the 5 parts of Pigment Blue 5 replaced by 5 parts of Pigment Red 81       *used as wet presscake material                                               **capable of effecting emulsion                                               .sup.1 sodium salt of a sulfate ester of an alkylphenoxy                      poly(ethyleneoxy)ethanol (28% active)                                         .sup.2 octylphenoxy polyethony ethanol (70% active)                           .sup.3 N-tallow trimethylene diamine (85% active)                             .sup.4 sodium salt of a condensed napthaline sulfonic acid                    .sup.5 azobisisobutyronitrile                                                 HiSil tradename for PPG Industries precipitated silica                        TiPure tradename for DuPont titanium dioxide pigment                     

                                      TABLE 9                                     __________________________________________________________________________    Preparation of Intrachromoleucospheruloid Pigment Composition                 (parts by weight)                                                             Example No. 9-      1    2     3    4      5                                  __________________________________________________________________________    A. Micronizing Step                                                           1. Organic Color Pigment                                                         Class            Phthalo-                                                                           Vat   Azo  Quinacridone                                                                         Cond. Azo                                              cyanine                                                      Trade Name       Heliogen                                                                           Brilliant                                                                           Permant                                                                            Monastral                                                                            Chromoptal                                             Green A                                                                            Orange RK                                                                           Carmine                                                                            Red B  Red BR                                Color Index Name Green 7                                                                            Orange 7                                                                            Red 5                                                                              Violet 19                                                                            --                                    Color Index Number                                                                             74260                                                                              71105 12490                                                                              46500                                        Pigment, dry basis                                                                             20*  30*   35   15     25                                 2. Inorganic Pigment                                                             Trade Name       Paper                                                                              Reinforcing                                                                         Aerosil                                                                            Reinforcing                                                                          Paper                                                  Grade                                                                              Grade 300  Grade  Grade Sil-                                             Silica                                                                             Silica     Silica (Wet)                                                                         ica (Wet)                                              (Wet)                                                                              (Wet)                                                   Pigment, dry basis                                                                             40   50    50   30     30                                 3. Inorganic Pigment                                                             Trade Name       --   --    --   TiPure R941                                                                          Unitane 0310                                                           Slurry Dispersion - Pigment, dry                                                     basis -- -- -- 30 30               4. Surface Active Agent**                                                        Material (Trade Name)                                                         Alipal CO433.sup.1                                                                             38   --    18   --     --                                    Triton X405.sup.2                                                                              --   38    10   28     38                                    Monazoline T.sup.3                                                                             2    --    --   --     2                                     Tetraethylenepentamine                                                                         --   2     2    --     --                                    Monaquat TIBC.sup.4                                                                            --   --    --   2      --                                    Ammonium Hydroxide 28%                                                                         2    2     2    2      2                                  5. Water, quantity  498  578   583  493    573                                6. Micronizing Step                                                              Method           Sand Sand  Sand Sand   Sand                                  Time, hours, approx.                                                                           48   48    48   48     48                                    Temperature, ° C.                                                                       28   28    28   28     28                                    Average Particle Size                                                         Diameter (microns)                                                            of Composite     <0.2 <0.2  <0.2 <0.2   <0.2                                  Pigment                                                                    7. Separation, Screening (X)                                                                      X    X     X    X      X                                  8. Water, dilution  300  200   200  300    300                                9. Aqueous Pigment Composition                                                   (Disperion) Yield                                                                              900  900   900  900    1000                               B. Polymerization Step                                                        10.                                                                              Surface Active Agent**                                                        (a) Quantity, type                                                                             --   --    20.sup.2                                                                           20.sup.2                                                                             10.sup.2                              (b) Quantity, type                                                                             --   --    --   --     --                                    Water            --   --    --   --     --                                    Ammonium Hydroxide 28%                                                                         10   10    10   10     10                                 11a.                                                                             Monomer Material                                                              Non Crosslinking                                                              Styrene          80   --    40   20     40                                    Methylmethacrylate                                                                             --   75    20   25     20                                    4-vinylpyridine  15   --    10   5      --                                    Dimethylaminoethylmethacrylate                                                                 --   15    --   10     20                                 11b.                                                                             Monomer Material                                                              Crosslinking                                                                  Ethyleneglycoldimethacrylate                                                                   5    10    10   --     --                                    50% Divinylbenzene                                                                             5    --    --   20     20                                    Polymerization Initiator                                                      AZDN.sup.5       --   3     3    3      3                                     Cumene Hydroperoxide                                                                           3    --    --   --     --                                    Polymerization Conditions                                                     Time, hours, approx.                                                                           6    6     7    6      6                                     Temperature, ° C.                                                                       80   75    80   75     75                                    Conversion, approx 100% (X)                                                                    X    X     X    X      X                                     Intrachromoleucospheruloid                                                    Pigment Dispersion - yield                                                                     1015 1010  1010 1010   1120                                  Average Particle Size                                                         Diameter (microns)                                                                             <4.0 <4.0  <4.0 <4.0   <4.0                               __________________________________________________________________________     *used as wet presscake material                                               **capable of effecting emulsion polymerization                                .sup.1 sodium salt of a sulfate ester of an alkylphenoxy                      poly(ethyleneoxy)ethanol (28% active)                                         .sup.2 octylphenoxy polyethoxy ethanol (70% active)                           .sup.3 substituted imidazoline of tall oil (100% active)                      .sup.4 substituted imidazoline quaternized with benzyl chloride (100%         active)                                                                       .sup.5 azobisisobutyronitrile                                                 Aerosil tradename for Degussa Company pyrogenic silica                        TiPure tradename for DuPont titanium dioxide pigment                          Unitane tradename for American Cyanamid titanium dioxide pigment         

                                      TABLE 10                                    __________________________________________________________________________    Preparation of Intrachromoleucospheruloid Pigment Composition                 (parts by weight)                                                             Example No. 10-      1    2    3      4      5                                __________________________________________________________________________    A. Micronizing Step                                                           1. Organic color Pigment                                                         Class             Vat  Phthalo-                                                                           Azamethine                                                                           Quinacridone                                                                         Dioxazine                                                  cyanine                                                Trade Name        Perylene                                                                           Heliogen                                                                           Irgazin                                                                              Magenta                                                                              Carbazole                                             Red  Blue BG                                                                            Yellow 3RLT   Violet                              Color Index Name  Red 29                                                                             Blue 15                                                                            Yellow 110                                                                           Red 122                                                                              Violet 23                           Color Index Number                                                                              71140                                                                              74160                                                                              --     --     --                                  Pigment, dry basis                                                                              20   25*  25     20     15*                              2. Inorganic Pigment                                                             Type or Trade Name     HiSil 233                                                                          HiSil 404                                                                            HiSil 233                                                                            HiSil 233                           Pigment, dry basis                                                                              --   30   20     20     20                               3. Inorganic Pigment                                                             Type              Titanium                                                                           Titanium                                                                           Titanium                                                                             Titanium                                                                             Titanium                                              Dioxide                                                                            Dioxide                                                                            Dioxide                                                                              Dioxide                                                                              Dioxide                                               Type 1.sup.a                                                                       Type 2.sup.b                                                                       Type 3.sup.c                                                                         Type 4.sup.d                                                                         Type 5.sup.e                        Pigment, dry basis                                                                              40   40   30     30     30                               4. Surface Active Agent**                                                        Material (Trade Name)                                                         Duomeen T.sup. 1  20   --   2      --     20                                  Monaquat TIBC.sup.2                                                                             --   20   --     --     --                                  Monazoline T.sup.3                                                                              --   --   --     --     --                                  Triton X400.sup.4 10   --   --     --     10                                  Triton X405.sup.5 --   --   20     20     10                                  Acetic Acid       10   --   --     --     --                                  Ammonium Hydroxide 28%                                                                          --   --   5      5      --                               5. Water, quantity   500  485  498    405    495                              6. Micronizing Step                                                              Method            Sand Sand Ball   Sand   Ball                                Time, hours, approx.                                                                            48   48   60     36     40                                  Temperature, ° C.                                                                        28   28   28     28     28                                  Average Particle Size                                                         Diameter (microns)                                                            of Composite      <0.1 <0.02                                                                              <0.2   <0.2   <0.2                                Pigment                                                                    7. Separation, Screening (X)                                                                       X    X    X      X      X                                8. Water, dilution   200  300  200    250    200                              9. Yield, Aqueous Pigment                                                        Composition (dispersion)                                                                        800  900  800    750    800                              B. Polymerization Step                                                        10.                                                                              Surface Active Agent**                                                        (a) Quantity, type                                                                              20.sup.2                                                                           25.sup.1                                                                           35.sup.5                                                                             35.sup.5                                                                             20.sup.1                            (b) Quantity, tupe                                                                              --   --   --     --     10.sup.4                            Water             75   65   55     55     60                                  Ammonium Hydroxide 28%                                                                          --   --   10     10     --                                  Acetic Acid       5    10   --     --     10                               11a.                                                                             MOnomer Material                                                              Non Crosslinking                                                              Styrene           20   --   20     --     60                                  Methylmethacrylate                                                                              20   40   --     20     --                                  Dimethylaminoethylmethacrylate                                                                  2    --   2      --     2                                   Cyclohexylmethacrylate                                                                          20   10   20     10     10                               11b.                                                                             Monomer Material                                                              Crosslinking                                                                  Ethyleneglycoldimethacrylate                                                                    10   5    5      5      5                                   Allylacrylate     --   5    --     --     5                                   Polymerization Initiator                                                      AZDN.sup.6        3    --   2      2      4                                   Cumene Hydroperoxide                                                                            --   3    --     --     --                                  Polymerization Conditions                                                     Time, hours, approx.                                                                            6    7    6      6      7                                   Temperature, °C.                                                                         75   80   75     75     85                                  Conversion, approx. 100% (X)                                                                    X    X    X      X      X                                   Intrachromoleucospheruloid                                                    Pigment Dispersion-yield                                                                        972  1060 947    885    982                                 Average Particle Size,                                                        Diameter (microns)                                                                              <4.0 <4.0 <4.0   <4.0   <4.0                             __________________________________________________________________________     Example 10-2-a. This example is made exactly as Example 10-2 accept           thatthe 30 parts of HiSil 233 are replaced by 30 parts of a wet               precipitated reinforcing grade silica containing 2% of a cationic amine       compound such as Armac T (Armour Chemical Company) slurried up therewith.     Example 10-3-a. This example is made exactly as Example 10-3n except that     the 30 parts of HiSil 404 are replaced by 30 parts of a wet precipitated      paper grade silica containing 2% of a water soluble polyamine i.e.            tetraethylenepentamine slurried up therewith.                                 Example 10-4-a. This example is made exactly as Example 10-4 except that      the 30 parts of titanium dioxide pigment type.sup.d are replaced by 30        parts of titanium dioxide pigment type.sup.f.                                 *used as wet presscake material                                               **capable of effecting emulsion polymerization                                .sup.1 N-tallow trimethylene diamine (85% active)                             .sup.2 substituted imidazoline quaternized with benzyl chloride (100%         active)                                                                       .sup.3 substituted imidazoline of tall oil (100% active)                      .sup.4 stearyl dimethyl benzyl ammonium chloride (82% active)                 .sup.5 octylphenoxy polyethoxy ethanol (70% active)                           .sup.6 azobisisobutyronitrile                                                 HiSil tradename for PPG Industries precipitated silica                        .sup.a Titanium dioxide pigment that has been slurried up in aqueous          dispersion with sufficient "N" type sodium silicate to produce on             acidification a titanium dioxide pigment composition containing 30% by        weight of precipitated silica thereon.                                        .sup.b Titanium dioxide pigment that has beenslurried up in queous            dispersion with sufficient titanium tetrachloride added so that the           resulting titanium dioxide pigment composition contains 10% by weight of      freshly precipitated titanium dioxide thereon.                                .sup.c Titanium dioxide pigment that has been slurried up in aqueous          dispersion with an aqueous dispersion of an aqueous resin slution             comprising equal molecular proportions of resorcinol and formaldehyde so      that the resulting titanium dioxide pigment composition contains 15% by       weight of the resorcinol/formaldehyde resin precipitated thereon.             .sup.d Titanium dioxide pigment that has been slurried up in aqueous          dispersion with an aqueous resin solution comprising equal molecular          proportions of urea and formaldehyde so that the resulting titanium           dioxide pigment composition contains 20% by weight of the                     urea/formaldehyde resin precipitated thereon.                                 .sup.e titanium dioxide pigment that has been slurried up in aqueous          dispersion with a water soluble organo silicon compound, i.e. Dow Corning     Z-6020 silane in sufficient quantity to provide a resulting titanium          dioxide pigment containing 2% by weight of the organo silane thereon.         .sup.f Titanium dioxide pigment that has been slurried up in aqueous          dispersion with a sufficient amount of a water dispersible                    polyethylenimine, i.e. Polyethylenimine 1800 to yield a resulting titaniu     dioxide pigment composition containing 5% by weight of the                    polyethylenimine precipitated thereon.                                   

TABLES 11-20

Preparation of Intrachromoleucospheruloid Pigment Material usingNoncross-linked Polymer Material.

                                      TABLE 11                                    __________________________________________________________________________    Preparation of Intrachromoleucospheruloid Pigment Composition                 (parts by weight)                                                             Example No. 11-       1      2      3      4      5                           __________________________________________________________________________    A.  Micronizing Step                                                          1.  Organic Color Pigment                                                         Class             Triphenyl-                                                                           Vat    Quinacridone                                                                         Azo    Phthalo-                                          methane              Pigment                                                                              cyanine                         Trade Name        Victoria                                                                             Indanthrene                                                                          Magenta                                                                              Carmine                                                                              Heliogen                        Blue              Red FBBA      FFY    Viridine Y                             Color Index Name  Blue 1 Red 10 Red 122                                                                              Red 5  Green 36                        Color Index Number                                                                              42595  6700.sup.0                                                                           --     12490  74160                           Pigment, dry basis                                                                              2      50     25*    30*    15*                         2.  Inorganic Pigment                                                             Trade Name        HiSil 404                                                                            Cab-O-Sil                                                                            HiSil 233                                                                            Excelopax                                                                            --                                                       H5            Zirconium                                                                     Silicate                               Pigment, dry basis                                                                              80     0.25   30     50     --                          3.  Inorganic Pigment                                                             Trade Name        Unitane                                                                              TiPure LW                                                                            Titanox RA                                                                           --     TiPure R941                                       OR450                       Slurry                          Pigment, dry basis                                                                              8      0.25    40    --     40                          4.  Surface Active Agent**                                                        Material, Trade Name                                                          Triton X405.sup.1 10     --     --     10     --                              Triton X305.sup.2 10     --     --     10     --                              Alipal C0433.sup.3                                                                              --     10     30     10     --                              Monaquat TIBC.sup.4                                                                             2      1      --     1      30                              Zonyl FSB.sup.5   1      0.5    --     1      1                               Ammonium Hydroxide 28%                                                                          10     --     10     5      --                              Acetic Acid       --     5      --     --     10                          5.  Water, quantity   377    333    365    383    304                         6.  Micronizing Step                                                              Method            Sand   Sand   Sand   Sand   Ball                            Time, hours, approx.                                                                            36     48     36     36     60                              Temperature, ° C.                                                                        28     28     28     28     28                              Average Particle size,                                                        Diameter (microns)                                                            of Composite      <0.2   <0.2   <0.2   <0.2   <0.2                            Pigment                                                                   7.  Separation, Screening (X)                                                                       X      X      X      X      X                           8.  Water, dilution   500    200    300    300    300                         9.  Yield Aqueous Pigment                                                         Composition (Dispersion)                                                                        1000   600    800    800    700                         B.  Polymerization Step                                                       10. Surface Active Agent**                                                        (a) Quantity, type                                                                              110.sup.1                                                                            40.sup.1                                                                             70.sup.3                                                                             30.sup.1                                                                             20.sup.1                        (b) Quantity, type                                                                              30.sup.3                                                                             20.sup.3                                                                             --     --     20.sup.4                        Water             50     35     20     70     50                              Acetic Acid       --     5      --     --     10                              Ammonium Hydroxide 28%                                                                          10     --     10     --     --                          11. Monomer Material                                                              Styrene           400    30     100    50     30                              Methylmethacrylate                                                                              380    60     --     --     50                              Dimethylaminoethylmethacrylate                                                                  20     10     --     --     --                              4-Vinylpyridine   --     --     20     10     --                              Acrylonitrile     --     --     --     30     --                              Acrylic Acid      --     --     --     --     10                          12. Polymerization Initiator                                                      AZDN.sup.6        --     3      --     3      4                               Potassium Persulfate                                                                            30     --     3      --     --                              Sodium Bisulfite  15     --     1.5    --     --                          13. Polymerization Conditions                                                     Time, hours, approx.                                                                            10     6      6      6      6                               Temperature, °C.                                                                         60     80     65     80     65                              Conversion, approx. 100% (X)                                                                    X      X      X      X      X                           14. Intrachromoleucospheruloid                                                    Pigment Dispersion                                                            Yield             2000   800    1020   990    890                             Average Particle Size,                                                        Diameter (microns)                                                                              <4.0   <4.0   <4.0   <4.0   <4.0                        __________________________________________________________________________     *used as wet presscake material                                               **capable of effecting emulsion polymerization                                HiSil tradename for PPG Industries precipitated silica                        Cab-O-Sil tradename for Cabot Corporation pyrogenic silica                    Excelopax tradename for National Lead Industries zirconium silicate           Unitane tradename for American Cyanamid Company titanium dioxide pigment      TiPure tradename for DuPont titanium dioxide pigment                          Titanox tradename for National Lead Industries titanium dioxide pigment       .sup.1 octylphenoxy polyethoxy ethanol (70% active)                           .sup.2 octylphenoxy polyethoxy ethanol (70% active)                           .sup.3 sodium salt of a sulfate ester of an alkylphenoxy                      poly(ethyleneoxy)ethanol (28% active)                                         .sup.4 substituted imidazoline quaternized with benzyl chloride (100%         active)                                                                       .sup.5 fluorochemical surface active agent                                    .sup.6 azobisisobutyronitrile                                            

                                      TABLE 12                                    __________________________________________________________________________    Preparation of Intrachromoleucospheruloid Pigment Composition                 (parts by weight)                                                             Example No. 12-       1      2      3      4      5                           __________________________________________________________________________    A.  Micronizing Step                                                          1.  Organic Color Pigment                                                         Class             Azamethine                                                                           Vat    Phthalo-                                                                             Dioxazine                                                                            Misc.                                                           cyanine                                       Trade Name        Irgazin                                                                              Perylene                                                                             Polymon                                                                              Heliogen                                                                             Naphtol                                           Yellow Red    Blue G Violet Green B                                           2GLT                                                        Color Index Name  Yellow 109                                                                           Red 29 Blue 16                                                                              Violet 23                                                                            Green 8                         Color Index Number                                                                              --     71140  74100  51319  10006                           Pigment, dry basis                                                                              25     30     25     15*    30                          2.  Inorganic Pigment                                                             Trade Name        HiSil 404                                                                            Micro-Cel                                                                            A-Sil-Ate                                                                            Cab-O-Sil                                                                            Santocel                                                 T-38   W      M-5    62                              Pigment, dry basis                                                                              20     40     30     25     40                          3.  Inorganic Pigment                                                             Trade Name        TiPure LW                                                                            --     --     --     --                              Pigment, dry basis                                                                              20     --     --     --     --                          4.  Surface Active Agent**                                                        Material (Trade Name)                                                         Triton X400.sup.1 --     --     --     25     --                              Triton X405.sup.2 80     --     40     --     30                              Duomeen T.sup.3   --     20     --     --     --                              Monazoline T.sup.4                                                                              1      --     1      --     1                               Ammonium Hydroxide 28%                                                                          10     --     --     --     --                              Acetic Acid       --     10     5      10     2                           5.  Water, quantity   345    400    399    325    397                         6.  Micronizing Step                                                              Method            Sand   Ball   Sand   Ball   Sand                            Time, hours, approx.                                                                            48     48     36     60     48                              Temperature, ° C.                                                                        28     28     28     28     28                              Average Particle Size,                                                        Diameter (microns)                                                            of Composite      <0.2   <0.1   <0.02  <0.02  <0.1                            Pigment                                                                   7.  Separation, Screening (X)                                                                       X      X      X      X      X                           8.  Water, dilution   300    300    300    300    300                         9.  Yield Aqueous Pigment                                                         Composition (Dispersions)                                                                       800    800    800    700    800                         B.  Polymerization Step                                                       10. Surface Active Agent**                                                        (a) Quantity, type                                                                              200.sup.2                                                                            20.sup.3                                                                             20.sup.2                                                                             25.sup.1                                                                             50.sup.2                        (b) Quantity, type                                                                              --     10.sup.4                                                                             --     10.sup.4                                                                             --                              Water             --     60     80     55     50                              Acetic Acid       --     10     --     10     --                              Ammonium Hydroxide 28%                                                                          20     --     --     --     --                          11. Monomer Material                                                              Styrene           19     40     --     78     60                              Methylmethacrylate                                                                              --     20     50     --     --                              Cyclohexylmethacrylate                                                                          --     20     20     --     18                              Dimethylaminoethylmethacrylate                                                                  1      --     --     2      2                           12. Polymerization Initiator                                                      AZDN.sup.5        1      3      3      3      3                               Cumene Hydroperoxide                                                                            2      --     --     --     --                          13. Polymerization Conditions                                                     Time, hours, approx.                                                                            4      5      6      6      5                               Temperature, ° C.                                                                        80     80     75     75     80                              Conversion, approx. 100% (X)                                                                    X      X      X      X      X                           14. Intrachromoleucospheruloid                                                    Pigment Dispersion                                                            yield             1040   980    970    880    980                             Average Particle Size,                                                        Diameter (microns)                                                                              <4.0   <4.0   <4.0   <4.0   <4.0                        __________________________________________________________________________     *used as wet presscake material                                               **capable of effecting emulsion polymerization                                HiSil tradename for PPG Industries precipitated silica                        Micro-Cel tradename for Johns-Mansville calcium silicate                      A-Sil-Ate tradename for Freeport Kaolin Company aluminum silicate             Cab-O-Sil tradename for Cabot Corporation pyrogenic silica                    Santocel tradename for Monsanto Corporation aerogel silica                    TiPure tradename for DuPont titanium dioxide pigment                          .sup.1 stearyl dimethyl benzyl ammonium chloride (82% active)                 .sup.2 octylphenoxy polyethoxy ethanol (70% active)                           .sup.3 N-tallow trimethylene diamine (85% active)                             .sup.4 substituted imidazoline of tall oil (100% active)                      .sup.5 azobisisobutyronitrile                                            

                                      TABLE 13                                    __________________________________________________________________________    Preparation of Intrachromolecuspheruloid Pigment Composition                  (parts by weight)                                                             Example No. 13-       1      2      3      4      5                           __________________________________________________________________________    A.  Micronizing Step                                                          1.  Organic Color Pigment                                                         Class             Vat    Azamethine                                                                           Quinacridone                                                                         Phthalo-                                                                             Azo                                                                    cyanine                                Trade Name        Ponsol Jade                                                                          Irgazin                                                                              Monastral                                                                            Heliogen                                                                             Hansa                                             Green  Orange RLT                                                                           Red Y  Green B                                                                              Yellow 3R                       Color Index Name  Green 1                                                                              Orange 42                                                                            Violet 19                                                                            Green 7                                                                              Orange 1                        Color Index Number                                                                              59825  --     46500  74260  11725                           Pigment, dry basis                                                                              30*    30     25     30*    35                          2.  Inorganic Pigment                                                             Trade Name        HiSil 404                                                                            TiPure R941                                                                          Unitane                                                                              Titanox                                                                              Horsehead                                                Slurry OR 450 RA47   R771                            Pigment, dry basis                                                                              40     30     30     40     40                          3.  Inorganic Pigment                                                             Trade Name        Cab-O-Sil                                                                            HiSil EP                                                                             HiSil 233                                                                            --     --                                                H5                                                          Pigment, dry basis                                                                              20     20     20     --     --                          4.  Surface Active Agent**                                                        Material, Trade Name                                                          Alipal C0433.sup.1                                                                              90     10     --     --     --                              Triton X405.sup.2 --     50     40     --     10                              Duomeen I.sup.3   --     --     --     25     20                              Monazoline I.sup.4                                                                              2      --     2      --     --                              Zonyl FSA.sup.5   1      --     1      --     --                              Zonyl FSC.sup.6   --     --     --     1      1                               Ammonium hydroxide 28%                                                                          10     10     5      --     --                              Acetic Acid       --     --     --     12     10                          5.  Water, Quantity   407    350    377    392    384                         6.  Micronizing Step                                                              Method            Sand   Sand   Sand   Ball   Ball                            Time, Hours, approx.                                                                            48     48     48     60     60                              Temperature, ° C.                                                                        28     28     28     28     28                              Average Particle Size                                                         Diameter (microns)                                                            of Composite      <0.1   <0.2   <0.1   <0.02  <0.1                            Pigment                                                                   7.  Separation, Screening (X)                                                                       X      X      X      X      X                           8.  Water, dilution   300    300    300    200    200                         9.  Yield Aqueous Pigment                                                         Composition (Dispersion)                                                                        900    800    800    700    700                         B.  Polymerization Step                                                        10.                                                                              Surface Active Agent**                                                        (a) Quantity, type                                                                              20.sup.2                                                                             25.sup.1                                                                             25.sup.1                                                                             25.sup.3                                                                             45.sup.2                        (b) Quantity, type                                                                              --     --     20.sup.2                                                                             --     15.sup.4                        Water             25     25     15     63     30                              Acetic Acid       --     --     --     12     10                              Ammonium Hydroxide 28%                                                                          5      10     10     --     --                          11. Monomer Material                                                              Styrene           --     60     --     35     50                              Methylmethacrylate                                                                              --     15     40     20     --                              Acrylonitrile     --     10     --     10     10                              Vinyltoluene      75     --     --     --     --                              4-Vinylpyridine   5      5      --     --     --                              Methacrylic Acid  --     --     --     5      --                          12. Polymerization Initiator                                                      AZDN.sup.7        3      3      2      --     3                               Cumene Hydroperoxide                                                                            --     --     2      3      --                          13. Polymerization Conditions                                                     Time, hours, approx.                                                                            7      6      6      7      5                               Temperature, ° C.                                                                        75     80     80     75     85                              Conversion, approx. 100% (X)                                                                    X      X      X      X      X                           14. Intrachromoleucospheruloid                                                    Pigment Dispersion-yield                                                                        1030   950    910    870    860                             Average Particle Size                                                         Diameter (microns)                                                                              <4.0   <4.0   <4.0   <4.0   <4.0                        __________________________________________________________________________     *used as wet presscake material                                               **capable of effecting emulsion polymerization                                HiSil tradename for PPG Industries precipitated silica                        Cab-O-Sil tradename for Cabot Corporation pyrogenic silica                    TiPure tradename for DuPont titanium dioxide pigment                          Unitane tradename for American Cyanamid Company titanium dioxide pigment      Titanox tradename for National Lead Industries titanium dioxide pigment       Horsehead tradename for New Jersey Zinc Company titanium dioxide pigment      .sup.1 sodium salt of a sulfate ester of an alkylphenoxy                      poly(ethyleneoxy)ethanol (28% active)                                         .sup.2 octylphenoxy polyethoxy ethanol (70% active)                           .sup.3 N-tallow trimethylene diamine (85% active)                             .sup.4 substituted imidazoline of tall oil (100% active)                      .sup.5 fluorochemical surface active agent (50% active)                       .sup.6 fluorochemical surface active agent (50% active)                       .sup.7 azobisisobutyronitrile                                            

                                      TABLE 14                                    __________________________________________________________________________    Preparation of Intrachromoleucospheruloid Pigment Composition                 (parts by weight)                                                             Example No. 14-       1      2      3      4      5                           __________________________________________________________________________    A.  Micronizing Step                                                          1.  Organic Color Pigment                                                         Class             Phthalo-                                                                             Cond. Azo                                                                            Dioxazine                                                                            Vat    Azamethine                                        cyanine                                                     Trade Name        Heliogen                                                                             Chromoptal                                                                           Irgazin                                                                              Sandothrene                                                                          Irgazin                                           Blue PG                                                                              Red BR Violet 6 RLT                                                                         Blue NCCD                                                                            Red 2 BLT                       Color Index Name  Blue 15                                                                              --     --     Blue 14                                                                              Red 180                         Color Index Number                                                                              74160  --     --     69810                                  Pigment, dry basis                                                                              20*    30     20     35     30                          2.  Inorganic Pigment                                                             Trade Name        Tronex Unitane                                                                              TiPure R960                                                                          Unitane                                                                              Barium                                            CR800  OR640         OR520  Sulfate                                                                       Pigment                                                                       White 5                         Pigment, dry basis                                                                              30     40     30     40     20                          3.  Inorganic Pigment                                                             Trade Name        Zinc Oxide                                                                           Cab-O-Sil                                                                            HiSil 404                                                                            Silene EF                                                                            TiPure R941                                       Pigment                                                                              H5                   Slurry                                            White 4                                                     Pigment, dry basis                                                                              15     20     20     20     30                          4.  Surface Active Agent**                                                        Material, Trade Name                                                          Alipal CO433.sup.1                                                                              20     --     --     --     30                              Triton X405.sup.2 20     10     20     --     10                              Duomac T.sup.3    --     20     --     40     --                              Monaquat TIBC.sup.4                                                                             2      --     20     --     2                               Zonyl FSB.sup.5   --     1      --     --     1                               Tamol SN.sup.6    2      --     --     --     --                              Ammonium Hydroxide 28%                                                                          10     --     --     --     --                              Acetic Acid       --     10     10     20     --                          5.  Water, quantity   381    370    380    395    377                         6.  Micronizing Step                                                              Method            Sand   Ball   Ball   Ball   Sand                            Time, hours, approx.                                                                            48     60     48     60     48                              Temperature, ° C.                                                                        28     28     28     28     28                              Average Particle Size,                                                        Diameter (microns)                                                            of Composite      <0.1   <0.1   <0.1   <0.2   <0.2                            Pigment                                                                   7.  Separation, Screening (X)                                                                       X      X      X      X      X                           8.  Water, dilution   300    200    200    250    300                         9.  Yield Aqueous Pigment                                                         Composition (dispersion)                                                                        800    700    700    800    800                         B.  Polymerization Step                                                       10. Surface Active Agent**                                                        (a) Quantity, type                                                                              90.sup.1                                                                             20.sup.2                                                                             20.sup.2                                                                             40.sup.2                                                                             50.sup.1                        (b) Quantity, type                                                                              --     20.sup.3                                                                             30.sup.4                                                                             20.sup.4                                                                             20.sup.2                        Water             --     50     40     30     20                              Acetic Acid       --     10     10     10     --                              Ammonium Hydroxide 28%                                                                          10     --     --     --     10                          11. Monomer Material                                                              Methylmethacrylate                                                                              60     --     40     --     50                              Styrene           22     50     40     35     40                              Dimethylaminoethylmethacrylate                                                                  8      --     --     --     --                              Cycylohexylmethacrylate                                                                         --     10     --     20     --                              4-vinylpyridine   --     --     --     5      --                              Methacrylic Acid  --     --     --     --     10                          12. Polymerization Initiator                                                      AZDN.sup.7        3      --     3      --     3                               Potassium Persulfate                                                                            --     2.5    --     2.5    --                              Sodium Bisulfite  --     1.25   --     1.25   --                          13. Polymerization Conditions                                                     Time, hours, approx.                                                                            5      6      5      6      5                               Temperature, ° C.                                                                        80     60     80     65     75                              Conversion, approx. 100% (X)                                                                    X      X      X      X      X                           14. Intrachromoleucospheruloid                                                    Pigment Dispersion-yield                                                                        990    860    880    960    1000                            Average Particle Size                                                         Diameter (microns)                                                                              <4.0   <4.0   <4.0   <4.0   <4.0                        Example 14-1-a. This example is prepared exactly as in Example 14-1           except that 30 parts                                                          of titanium dioxide, Tronex CR800 are replaced by 30 parts of a natural       silica pigment,                                                               Min-U-Sil (product of PGS).                                                   Example 14-2-a. This example is prepared exactly as in Example 14-2           except that 20 parts                                                          of Cab-O-Sil H5 are replaced by 20 parts of zirconium silicate                "Excelopax" produced by                                                       NL. Tam. Div.)                                                                Example 14-2-b. This example is prepared exactly as in Example 14-2           except that the 20                                                            parts of Unitane OR640 are replaced by 20 parts of Zirconium Oxide,           pigment white 12                                                              (manufactured by NL. Tam. Div.)                                               Example 14-2-c. This example is prepared exactly as in Example 14-2           except that the 20                                                            parts of Cab-O-Sil H5 are replaced by 20 parts of alumina hydrate             (manufactured by Alcoa).                                                      Example 14-5-a. This example is prepared exactly as in Example 14-5           except that the 20                                                            parts of Barium Sulfate Pigment White 5 are replaced by 20 parts of           Celite 110, a natural                                                         silica pigment (manufactured by Johns-Mansville Company).                     Example 14-5-b. This example is prepared exactly as in Example 14-5           except that the 20                                                            parts of Barium Sulfate, Pigment White 5, are replaced by 20 parts of         Pigment White 20,                                                             Aluminum Potassium Silicate.                                                  __________________________________________________________________________     *used as wet presscake material                                               **capable of effecting emulsion polymerization                                Tronex tradename for Kerr-McGee Company titanium dioxide pigment              Unitane tradename for American Cyanamid Company titanium dioxide pigment      TiPure tradename for DuPont titanium dioxide pigment                          Cab-O-Sil tradename for Cabot Corporation pyrogenic silica                    Silene EF tradename for PPG Industries precipitated silica, calcium           modified                                                                      HiSil tradename for PPG Industries precipitated silica                        .sup.1 sodium salt of a sulfate ester of an alkylphenoxy                      poly(ethyleneoxy)ethanol (28% active)                                         .sup.2 octylphenoxy polyethoxy ethanol (70% active)                           .sup.3 N-tallow trimethylene diamine diacetate (85% active)                   .sup.4 substituted imidazoline quaternized with benzyl chloride (100%         active)                                                                       .sup.5 fluorochemical surface active agent (50% active)                       .sup.6 sodium salt of a condensed naphthalene sulfonic acid                   .sup.7 azobisisobutyronitrile                                            

                                      TABLE 15                                    __________________________________________________________________________    Preparation of Intrachromoleucospheruloid Pigment Composition                 (parts by weight)                                                             Example No. 15-       1      2      3      4      5                           __________________________________________________________________________    A.  Micronizing Step                                                          1.  Organic Color Pigment                                                         Class             Phthalo-                                                                             Phthalo-                                                                             Vat    Vat    Azamethine                                        cyanine                                                                              cyanine                                              Trade Name        Viridine                                                                             Polymon                                                                              Indanthrene                                                                          Indanthrene                                                                          Yellow                                            Ex. Y  Blue G Pink R Rubine R                                                                             2 GLT                           Color Index Name  Green 41                                                                             Blue 16                                                                              Red 1  Red 13 Yellow 109                      Color Index Number                                                                              --     74100  73360  70320  --                              Pigment, dry basis                                                                              25*    30     30*    35     25                          2.  Inorganic Pigment                                                             Trade Name        Celite 281                                                                           Micro-Cel                                                                            Al-Sil-Ate                                                                           Excelopax                                                                            Baroid                                                   T70    H0     Zirconium                                                                            Macaloid                                                               silicate                               Pigment, dry basis                                                                              20     30     40     40     10                          3.  Inorganic Pigment                                                             Trade Name        Titanox                                                                              Unitane                                                                              TiPure TiPure Titanox                                           RA     OR220  R941   R900   RA                              Pigment, dry basis                                                                              30     40     40     50     30                          4.  Surface Active Agent**                                                        Material, Trade Name                                                          Triton X305.sup.1 20     --     10     --     --                              Triton X400.sup.2 --     20     --     20     --                              Triton X405.sup.3 20     20     30     --     20                              Tamol SN.sup.4     2     --      1     --     --                              Monazoline T.sup.5                                                                               2     --      1     20      1                              Ammonium Hydroxide 28%                                                                          --     --     --     --                                     Acetic Acid       --      5      5     10                                 5.  Water, quantity   331    355    343    325    309                         6.  Micronizing Step                                                              Method            Sand   Sand   Sand   Ball   Sand                            Time, hours, approx.                                                                            36     24     36     60     48                              Temperature, ° C.                                                                        28     28     28     28     28                              Average Particle Size                                                         Diameter (microns)                                                            of Composite      <0.1   <0.1   <0.2   <0.1   <0.2                            Pigment                                                                   7.  Separation, Screening (X)                                                                       X      X      X      X      X                           8.  Water, dilution   250    200    200    200    200                         9.  Yield Aqueous Pigment                                                         Composition (dispersion)                                                                        700    700    700    700    600                         B.  Polymerization Step                                                       10. Surface Active Agent**                                                        (a) Quantity, type                                                                              --     20.sup.3                                                                             --     20.sup.5                                                                             40.sup.3                        (b) Quantity, type                                                                              --     --     --     --     --                              Water             --     20     --     70     35                              Acetic Acid       --     10     --     10     --                              Ammonium Hydroxide 28%                                                                          10     --     --     --     25                          11. Monomer Material                                                              Vinyltoluene      75     --     60     60     78                              4-Vinylpyridine    5      5     10       10.05                                                                              --                              Methacrylic acid  --     --     --       8.5  20                              Methylmethacrylate                                                                               5     10     --     10     20                              Dimethylaminoethylmethacrylate                                                                   5      5     --      1      2                              Styrene                                                                   12. Polymerization Initiator                                                      AZDN.sup.6        --     --      3      4      4                              Cumene Hydroperoxide                                                                             3      3     --     --     --                          13. Polymerization Conditions                                                     Time, hours, approx.                                                                             6      5      5      6      7                              Temperature, ° C.                                                                        90     80     80     75     90                              Conversion, approx. 100% (X)                                                                    X      X      X      X      X                           14. Intrachromoleucospheruloid                                                    Pigment Dispersion                                                            yield             800    840    800    900    800                             Average Primary Particle                                                      Size Diameter (microns)                                                                         <4.0   <4.0   <4.0   <4.0   <4.0                        Example 15-1-a. This example is prepared exactly as Example 15-1 except       that the 30 parts                                                             of titanium dioxide are replaced by 20 parts of magnesium oxide.              Example 15-1-b. This example is prepared exactly as Example 15-1 except       that the 30 parts                                                             of titanium dioxide are replaced by 30 parts of alumina. -Example 15-1-c.     This example is prepared exactly as in Example 15-1 except that the 20        parts of silica (Celite 281) are replaced by 20 parts of hydrated             aluminum oxide.                                                               Example 15-3-a. This example is prepared exactly as in Example 15-3           except that the 40                                                            parts of titanium dioxide are replaced by 40 parts of antimony oxide.         Example 15-3-b. This example is prepared exactly as in Example 15-3           except that the 40                                                            parts of titanium dioxide are replaced with 40 parts of zinc oxide.           Example 15-5-a. This example is prepared exactly as Example 15-5 except       that the 40 parts                                                             of titanium dioxide are replaced with 40 parts of zirconium                   __________________________________________________________________________    oxide.                                                                         *used as wet presscake material                                               **capable of effecting emulsion polymerization                                Celite tradename for Johns-Mansville Company natural silica                   Micro-Cel tradename for Johns-Mansville Company calcium silicate              A-Sil-Ate tradename for Freeport Kaolin Company aluminum silicate             Excelopax tradename for NL Industries zirconium silicate                      Baroid Macaloid tradename for NL industries magnesium silicate                Titanox tradename for NL Industries titanium dioxide pigment                  Unitane tradename for American Cyanamid Company titanium dioxide pigment      TiPure tradename for DuPont titanium dioxide pigment                          .sup.1 octylphenoxy polyethoxy ethanol (70% active)                           .sup.2 stearyl dimethyl benzyl ammonium chloride (82% active)                 .sup.3 octylphenoxy polyethoxy ethanol (70% active)                           .sup.4 sodium salt of a condensed naphthalene sulfonic acid                   .sup.5 N-tallow trimethylene diamine (85% active)                             .sup.6 azobisisobutyronitrile                                            

                                      TABLE 16                                    __________________________________________________________________________    Preparation of Intrachromoleucospheruloid Pigment Composition                 (parts by weight)                                                             Example No. 16-       1      2      3      4      5                           __________________________________________________________________________    A.  Micronizing Step                                                          1.  Organic Color Pigment                                                         Class             Phthalo-                                                                             Vat    Phthalo-                                                                             Vat    Azamethine                                        cyanine       cyanine                                       Trade Name        Heliogen                                                                             Ponsol Heliogen                                                                             Indanthrene                                                                          Irgazin                                           Green A                                                                              Jade Green                                                                           Blue PG                                                                              Red FBBA                                                                             Red 2 BLT                       Color Index Name  Green 7                                                                              Green 1                                                                              Blue 15                                                                              Red 10 Red 180                         Color Index Number                                                                              74260  59826  74160  67009  --                              Pigment, dry basis                                                                              25*    20*    25*    30*    25                          2.  Inorganic Pigment                                                             Trade Name        HiSil 233                                                                            HiSil 404                                                                            Cab-O-Sil                                                                            Ludox Coll-                                                                          HiSil 233                                                       M5     oidal Silica                           Pigment, dry basis                                                                              20     20     20     20     20                          3.  Inorganic Pigment                                                             Trade Name        Multiflex                                                                            Hydral 705                                                                           Oncor 23A                                                                            Zirconium                                                                            Zinc Oxide,                                       MM                   Oxide  Pigment                                                                       White 4                         Pigment, dry basis                                                                              30     30     30     30     30                          4.  Surface Active Agent**                                                        Material (Trade Name)                                                         Triton X305.sup.1 20     --     --     20     20                              Triton X400.sup.2 20     --      4     --     --                              Alipal CO433.sup.3                                                                              --     --     26     20     --                              Tamol SN.sup.4    --     --      2      2     --                              Duomeen T.sup.5   --     20     --     --     20                              Ammonium Hydroxide 28%                                                                          --     --     --     10     --                              Acetic Acid       10     10     --     --     10                          5.  Water, quantity   475    400    393    368    455                         6.  Micronizing Step                                                              Method            Ball   Ball   Sand   Sand   Ball                            Time, hours, approx.                                                                            60     60     48     48     46                              Temperature, ° C.                                                                        28     28     28     28     28                              Average Particle Size,                                                        Diameter (microns)                                                            of Composite      <0.2   <0.2   <0.1   <0.2   <0.2                            Pigment                                                                   7.  Separation, Screening (X)                                                                       X      X      X      X      X                           8.  Water, dilution   200    200    200    200    200                         9.  Yield Aqueous Pigment                                                         Composition (dispersion)                                                                        800    700    700    700    800                         B.  Polymerization Step                                                       10. Surface Active Agent**                                                        (a) Quantity, type                                                                              20.sup.1                                                                             30.sup.5                                                                             50.sup.3                                                                             20.sup.3                                                                             20.sup.1                        (b) Quantity, type                                                                              20.sup.2                                                                             --     --     --     20.sup.5                        Water             50     55     40     70     50                              Acetic Acid       10     15     --     --     10                              Ammonium Hydroxide 28%                                                                          --     --     10     10     --                          11. Monomer Material                                                              Styrene           40     20     20     40     30                              Methylmethacrylate                                                                              --     50     20     --     30                              Dimethylaminoethylmethacrylate                                                                  --     --     20     --     --                              4-Vinylpyridine   --     --     --     10     --                              Methacrylic Acid   5      5     --     --     --                              Acrylic Acid      --     --     --     --      5                          12. Polymerization Initiator                                                      AZDN.sup.6        --     --      3      3     --                              Potassium Persulfate                                                                            2.5     3     --     --     2.5                             Sodium Bisulfite  1.25   1.5    --     --     1.25                        13. Polymerization Conditions                                                     Time, hours, approx.                                                                             5      6      5      5      6                              Temperature, ° C.                                                                        65     65     80     80     65                              Conversion, approx. 100% (X)                                                                    X      X      X      X      X                           14. Intrachromoleucospheruloid                                                    Pigment Dispersion                                                            yield             945    875    860    850    965                             Average Particle Size                                                         Diameter (microns)                                                                              <4.0   <4.0   <4.0   <4.0   <4.0                        __________________________________________________________________________     *used as wet presscake material                                               **capable of effecting emulsion polymerization                                HiSil tradename for PPG Industries precipitated silica                        Cab-O-Sil tradename for Cabot Corporation pyrogenic silica                    Ludox tradename for DuPont colloidal silica                                   Multilfex tradename for Diamond Shamrock Corporation calcium carbonate        Hydral tradename for Alcoa hydrated aluminum oxide                            Oncor tradename for NL Industries antimony oxide pigment                      .sup.1 octylphenoxy polyethoxy ethanol (70% active)                           .sup.2 stearyl dimethyl benzyl ammonium chloride (82% active)                 .sup.3 sodium salt of a sulfate ester of an alkylphenoxy                      poly(ethyleneoxy)ethanol (28% active)                                         .sup.4 sodium salt of a condensed naphthalene sulfonic acid                   .sup.5 N-tallow trimethylene diamine (85% active)                             .sup.6 azobisisobutyronitrile                                            

                                      TABLE 17                                    __________________________________________________________________________    Preparation of Intrachromoleucospheruloid Pigment Composition                 (parts by weight)                                                             Example No. 17-       1      2      3      4      5                           __________________________________________________________________________    A.  Micronizing Step                                                          1.  Organic Color Pigment                                                         Class             Dioxazine                                                                            Vat    Triphenyl-                                                                           Phthalo-                                                                             Azo                                               Carbazole                                                                            Perylene                                                                             methane                                                                              cyanine                                Trade Name        Violet R                                                                             Red    Victoria                                                                             Viridine                                                                             Ex.Y Permagen                                                   Blue                                          Color Index Name  Violet 23                                                                            Red 29 Blue 1 Green 41                                                                             Yellow 14                       Color Index Number                                                                              51319  71140  42595  74160  21095                           Pigment, dry basis                                                                              15*    30*    20     30     35                          2.  Inorganic Pigment                                                             Trade Name        Titanox                                                                              Unitane                                                                              TiPure LW                                                                            TiPure R941                                                                          TiPure                                            RA 45  OR560         Slurry R900                            Pigment, dry basis                                                                              25     40     30     40     45                          3.  Inorganic Pigment                                                             Trade Name        Silene D                                                                             HiSil EP                                                                             Excelopax                                                                            HiSil 233                                                                            Oncor 23A                                                       Zirconium                                                                     Silicate                                      Pigment, dry basis                                                                              15     20     15     20     10                          4.  Surface Active Agent**                                                        Material, Trade Name                                                          Triton X405.sup.1 100    --     --     --     --                              Alipal CO433.sup.2                                                                              --     20     --     --     --                              Tamol 731.sup.3   --     15     --     --     --                              Monazoline T.sup.4                                                                               2      2     10     --     --                              SAMV Amphoteric Copolymer.sup.5                                                                 --     --     40     --     --                              SMA Copolymer.sup.6                                                                             --     --     --     30     --                              N-Group polymer.sup.7                                                                           --     --     --     --     40                              Ammonium Hydroxide 28%                                                                          2       5     --      5      5                              Acetic Acid       --     --      5     --     --                          5.  Water, Quantity   341    368    380    375    365                         6.  Micronizing Step                                                              Method            Sand   Sand   Sand   Sand   Sand                            Time, hours, approx.                                                                            48     48     48     48     48                              Temperature, ° C.                                                                        28     28     28     28     28                              Average Particle Size                                                         Diameter (microns)                                                            of Composite      <0.1   <0.1   <0.2   <0.1   <0.1                            Pigment                                                                   7.  Separation, Screening (X)                                                                       X      X      X      X      X                           8.  Water, dilution   200    200    200    200    200                         9.  Yield Aqueous Pigment                                                         Composition (dispersion)                                                                        700    700    700    700    700                         B.  Polymerization Step                                                       10. Surface Active Agent**                                                        (a) Quantity, type                                                                              --     60.sup.2                                                                             20.sup.1                                                                             70.sup.2                                                                             50.sup.1                        (b) Quantity, type                                                                              --     --     20.sup.4                                                                             --     --                              Water             --     30     25     25     45                              Acetic Acid       --     --      5     --     --                              Ammonium Hydroxide 28%                                                                           5     10     --      5     5                           11. Monomer Material                                                              Styrene           50     60.9   50     --     --                              4-vinylpyridine   10     10.5   --     --     --                              Methacrylic Acid  --      8.6   --     --     --                              Acrylonitrile     --     --     10     --     --                              Dimethylaminoethylmethacrylate                                                                  --     --     --     15     15                              Methylmethacrylate                                                                              --     --     --     45     45                          12. Polymerization Initiator                                                      AZDN.sup.8         2      3      2     --      2                              Cumene Hydroperoxide                                                                            --     --     --      3     --                          13. Polymerization Conditions                                                     Time, hours, approx.                                                                             4      5      4      4       4                             Temperature, ° C.                                                                        80     80     85     80     80                              Conversion, approx. 100% (X)                                                                    X      X      X      X      X                           14. Intrachromoleucospheruloid                                                    Pigment Dispersion-yield                                                                        765    880    830    860    860                             Average Particle Size                                                         Diameter (microns)                                                                              <4.0   <4.0   <4.0   <4.0   <4.0                        __________________________________________________________________________     *used as wet presscake material                                               **capable of effecting emulsion polymeriation                                 Titanox tradename for National Lead Industries titanium dioxide pigment       Unitane tradename for American Cyanamid titanium dioxide pigment              TiPure tradename for DuPont titanium dioxide pigment                          Silene tradename for PPG Industries precipitated silica, calcium modified     HiSil tradename for PPG Industries precipitated silica                        Excelopax tradename for National Lead Industries zirconium silicate           Oncor tradename for National Lead Industries antimony oxide/silica pigmen     .sup.1 octylphenoxy polyethoxy ethanol (70% active)                           .sup.2 sodium salt of a sulfate ester of an alkylphenoxy                      poly(ethyleneoxy)ethanol (28% active)                                         .sup.3 sodium salt of a polycarboxylic acid (100% active)                     .sup.4 substituted imidazoline of tall oil (100% active)                      .sup.5 copolymer of styrene, acrylonitrile, methacrylic acid and              4-vinylpyridine, ratio 25/10/29/36                                            .sup.6 copolymer of styrene, methacrylic acid and acrylonitrile, ratio        25/65/10                                                                      .sup.7 4-vinylpyridine homopolymer                                            .sup.8 azobisisobutyronitrile                                            

                                      TABLE 18                                    __________________________________________________________________________    Preparation of Intrachromoleucospheruloid Pigment Composition                 (parts by weight)                                                             Example No. 18-       1      2      3      4      5                           __________________________________________________________________________    A.  Micronizing Step                                                          1.  Organic Color Pigment                                                         Class             Dioxazine                                                                            Phthalo-                                                                             Quinacridone                                                                         Azo    Vat                                                      cyanine                                              Trade Name        Irgazon                                                                              Heliogen                                                                             Magenta                                                                              Permanent                                                                            Indanthren                                        Violet 2BLT                                                                          Green A       Carmine                                                                              Blue BC                         Color Index Name  --     Green 7                                                                              Red 122                                                                              Red 5  Blue 6                          Color Index Number                                                                              --     74260  --     12490  69825                           Pigment, dry basis                                                                              20     20*    30     30     30*                         2.  Inorganic Pigment                                                             Trade Name        HiSil 404                                                                            Excelopax                                                                            Micro-Cel                                                                            Cab-O-Sil                                                                            HiSil 233                                                Zirconium                                                                            T-38   H5                                                              Silicate                                             Pigment, dry basis                                                                              20     20     30     25     25                          3.  Inorganic Pigment                                                             Trade Name        Oncor 23A                                                                            TiPure LW                                                                            TiPure R941                                                                          Aluminum                                                                             TiPure LW                                                       Slurry Oxide                                  Pigment, dry basis                                                                              30     30     40     40     40                          4.  Surface Active Agent**                                                        Material, Trade Name                                                          Alipal CO433.sup.1                                                                              40     --     --     20     --                              Monazoline T.sup. 2                                                                              2     --     --      2     --                              Zonyl FSH.sup.3    1     --     --      1     --                              Duomeen T.sup.4   --     30     --     --     30                              Monaquat TIBC.sup.5                                                                             --     10      2     --     10                              Triton X405.sup.6 --     --     50     --     --                              Ammonium Hydroxide 28%                                                                          10     --     --     --     --                              Acetic Acid       --     15     --     --     15                          5.  Water, Quantity   377    375    348    382    350                         6.  Micronizing Step                                                              Method            Sand   Ball   Sand   Sand   Ball                            Time, hours, approx.                                                                            48     60     48     48     60                              Temperature, ° C.                                                                        28     28     28     28     28                              Average Particle Size                                                         Diameter (microns)                                                            of Composite      <0.1   0.2-0.1                                                                              0.2-0.1                                                                              0.2-0.1                                                                              <0.2                            Pigment                                                                   7.  Separation, Screening (X)                                                                       X      X      X      X      X                           8.  Water, dilution   300    200    300    200    200                         9.  Yield Aqueous Pigment                                                         Composition (dispersion)                                                                        800    700    800    700    700                         B.  Polymerization Step                                                       10.  Surface Active Agent**                                                       (a) Quantity, type                                                                              40.sup.1                                                                             20.sup.5                                                                             50.sup.6                                                                             75.sup.6                                                                             20.sup.6                        (b) Quantity, type                                                                              50.sup.6                                                                             --     --     --     --                              Water             --     25     45     20     30                              Acetic Acid       --      5     --     --     --                              Ammonium Hydroxide 28%                                                                          10     --      5      5     --                          11. Monomer Material                                                              Styrene           50     --     40     --     30                              Cyclohexylmethacrylate                                                                          --     50     --     20     20                              Methylmethacrylate                                                                              --     --     --     20     30                              Vinyltoluene      --     --     20     --     --                              Dimethylaminoethylmethacrylate                                                                  10     --     10     10     --                              Methacrylic Acid  --     --     --     --     10                          12. Polymerization Initiator                                                      AZDN.sup.7         2     --      3      2     --                              Cumene Hydroperoxide                                                                            --      2     --     --      2                          13. Polymerization Conditions                                                     Time, hours, approx.                                                                             4      4      5      5      6                              Temperature, ° C.                                                                        80     80     80     80     80                              Conversion, approx. 100% (X)                                                                    X      X      X      X      X                           14. Intrachromoleucospheruloid                                                    Pigment Dispersion-yield                                                                        960    800    970    850    840                             Average Particle Size                                                         Diameter (microns)                                                                              <4.0   <4.0   <4.0   <4.0   <4.0                        15. Water, dilution, approx.                                                                        3000   3000   3000   3000   3000                        16. Coagulant, additive                                                                             30.sup.a                                                                             30.sup.b                                                                             30.sup.c                                                                             30.sup.d                                                                             30.sup.e                        Temperature, ° C.                                                  17. Reaction Temperature, ° C.                                                               80     80     80     80     80                          18. Reaction Time, hrs. approx.                                                                      6      6      6     6       6                          19. Isolation Method                                                              Filtration and washing (X)                                                                      --     X      X      --     X                           20. Product Available as                                                          Wet Coagulum (X)  --     X      X      --     X                           21. Drying Method (x)                                                             Oven              --     X      X      --     X                               Spray             X      --     --     X      --                          22. Dry Intrachromoleuco-                                                         spheruloid Pigment-                                                           yield (approx.)   154    130    170    203    195                         __________________________________________________________________________     *used as wet presscake material                                               **capable of effecting emulsion polymerization                                HiSil tradename for PPG Industries precipitated silica                        Excelopax tradename for NL Industries zirconium silicate                       Micro-Cel tradename for Johns-Mansville calcium silicate                     Cab-O-Sil tradename for Cabot Corporation pyrogenic silica                    Oncor tradename for NL Industries antimony oxide pigment                      TiPure tradename for DuPont titanium dioxide pigment                          .sup.1 sodium salt of a sulfate ester of an alkylphenoxy                      poly(ethyleneoxy)ethanol (28% active)                                         .sup.2 substituted imidazoline of tall oil (100% active)                      .sup.3 fluorochemical surface active agent (100% active)                      .sup.4 N-tallow trimethylene diamine (85% active)                             .sup.5 substituted imidazoline quaternized with benzyl chloride (100%         active)                                                                       .sup.6 octylphenoxy polyethoxy ethanol (70% active)                           .sup.7 azobisisobutyronitrile                                                 .sup.a acetic acid?                                                           .sup.b aq. NaOH                                                               .sup.c hydroxyacetic acid                                                     .sup.d formic acid                                                            .sup.e NH.sub.4 OH                                                       

                                      TABLE 19                                    __________________________________________________________________________    Preparation of Intrachromoleucospheruloid Pigment Composition                 (parts by weight)                                                             Example No. 19-       1               2                                       __________________________________________________________________________    A.  Micronizing Step                                                          1.  Organic Color Pigment                                                         Class             Azamethine                                                                            Phthalocyanine                                                                        CO433.sup.Triphenylmethane                  Trade Name        Irgazin Heliogen                                                                              Perylene                                                                            Permanent                                               Yellow 3 RLT                                                                          Blue BG Red   Rose T Toner                          Color Index Name  Yellow 110                                                                            Blue 15 Red 29                                                                              Red 81                                Color Index Number                                                                              --      74160   71140 45160                                 Pigment, dry basis                                                                              35      5*      30    10                                2.  Inorganic Pigment                                                             Trade Name        HiSil 233       HiSil 404                                   Pigment, dry basis                                                                              30                    30                                3.  Inorganic Pigment Unitane OR220   TiPure R                                                                            941 Slurry                            Pigment, dry basis                                                                              40                    40                                4.  Surface Active Agent**                                                        Material, Trade Name                                                          Alipal C0433.sup.1                                                                              10                    10                                    Triton X405.sup.2 20                    20                                    Tamol SN.sup.3    2                     2                                     Monazoline T.sup.4                                                                              3                     3                                     Ammonium Hydroxide 28%                                                                          5                     5                                 5.  Water, quantity   350                   350                               6.  Micronizing Step                                                              Method            Sand                  Sand                                  Time, hours, approx.                                                                            48                    48                                    Temperature, ° C.                                                                        28                    28                                    Average Particle Size                                                         Diameter (microns)                                                                              0.2-0.1               0.2-0.1                               of Composite                                                                  Pigment                                                                   7.  Separation, Screening (X)                                                                       X                     X                                 8.  Water, dilution   300                   300                               9.  Yield Aqueous Pigment                                                         Composition (dispersion)                                                                        800                   800                               B.  Polymerization Step                                                       10. Surface Active Agent**                                                        (a) Quantity, type                                                                              10.sup.1              10.sup.1                              (b) Quantity, type                                                                              40.sup.2              40.sup.2                              Water             40                    40                                    Acetic Acid       --                    --                                    Ammonium Hydroxide 28%                                                                          10                    10                                11. Monomer Material                                                              Styrene           40              --                                          Methylmethacrylate                                                                              60                                                          Dimethylaminoethylmethacrylate                                                                  10              10                                          Acrylonitrile     10              --                                          Cyclohexylmethacrylate                                                                          --              10                                      12. Polymerization Initiator                                                      AZDN.sup.5        --              3                                           Potassium Persulfate                                                                            3.0             --                                          Sodium Bisulfite  1.5             --                                      13. Polymerization Conditions                                                     Time, hours, approx.                                                                            6               6                                           Temperature, ° C.                                                                        80              80                                          Conversion, approx. 100% (X)                                                                    X               X                                       14. Intrachromoleucospheruloid                                                    Pigment Dispersion - yield                                                                      980             980                                         Average Particle Size                                                         Diameter (microns)                                                                              <4.0            <4.0                                    __________________________________________________________________________     *used as wet presscake material                                               **capable of effecting emulsion polymerization                                HiSil tradename for PPG Industries precipitated silica                        Unitane tradename for American Cyanamid titanium dioxide pigment              TiPure tradename for DuPont titanium dioxide pigment                          .sup.1 sodium salt of a sulfate ester of an alkylphenoxy                      poly(ethyleneoxy)ethanol (28% active)                                         .sup.2 octylphenoxy polyethoxy ethanol (70% active)                           .sup.3 sodium salt of a condensed napthalene sulfonic acid                    .sup.4 substituted imidazoline of tall oil (100% active)                      .sup.5 azobisisobutyronitrile                                            

                                      TABLE 20                                    __________________________________________________________________________    Preparation of Intrachromoleucospheruloid Pigment Composition                 (parts by weight)                                                             Example No. 20-       1      2      3      4      5                           __________________________________________________________________________    A.  Micronizing Step                                                          1.  Organic Color Pigment                                                         Class             Vat    Quinacridone                                                                         Cond.Azo                                                                             Azo    Phthalo-                                                                      cyanine                         Trade Name        Brilliant                                                                            Chromoptal                                                                           Permagen                                                                             Heliogen                                                 Orange RK                                                                            Red Y  Red BR Yellow Blue BG                         Color Index Name  Orange 7                                                                             Violet 19                                                                            --     Yellow 14                                                                            Blue 15                         Color Index Number                                                                              71105  46500  --     21095  74160                           Pigment, dry basis                                                                              30*    25     30     35     30                          2.  Inorganic Pigment Paper Grade                                                                          Reinforcing                                                                          Aerosel                                                                              Reinforcing                                                                          Paper Grade                     Trade Name        Silica Grade  300    Grade  Silica                                            Wet PP Wet PP        Silica Wet PP                                                                 Wet PP                                 Pigment, dry basis                                                                              60     40     50     60     60                          3.  Inorganic Pigment                                                             Trade Name        --     TiPure R941                                                                          Unitane                                                                              --     --                                                       Slurry 0310                                                                          Dispersion                                    Pigment, dry basis                                                                              --     30     30     --     --                          4.  Surface Active Agent**                                                        Material, Trade Name                                                          Alipal C0433.sup.1                                                                              --     --     --     10     20                              Triton X405.sup.2 40     40     40     30     20                              Monazoline T.sup.3                                                                              --     --     2      --     2                               Tetraethylenepentamine                                                                          2      --     --     --     --                              Monaquat TIBC.sup.4                                                                             --     2             2      --                              Ammonium Hydroxide 28%                                                                          2      2      2      2      2                           5.  Water, quantity   366    361    394    361    366                         6.  Micronizing Step                                                              Method            Sand   Sand   Sand   Sand   Sand                            Time, hours, approx.                                                                            48     48     48     48     48                              Temperature, ° C.                                                                        28     28     28     28     28                              Average Particle Size                                                         Diameter, (microns)                                                           of Composite      <0.1   <0.2   <0.2   <0.1   <0.1                            Pigment                                                                   7.  Separation, Screening (X)                                                                       X      X      X      X      X                           8.  Water, dilution   300    300    250    300    300                         9.  Yield Aqueous Pigment                                                         Composition (Dispersion)                                                                        800    800    800    800    800                         B.  Polymerization Step                                                       10. Surface Active Agent**                                                        (a) Quantity, type                                                                              20.sup.1                                                                             20.sup.1                                                                             20.sup.2                                                                             20.sup.2                                                                             20.sup.2                        (b) Quantity, type                                                                              --     --     --     --     --                              Water             70     70     70     70     70                              Acetic Acid       --     --     --     --     --                              Ammonium Hydroxide 28%                                                                          10     10     10     10     10                          11. Monomer Material                                                              Styrene           40     --     20     40     50                              Methylmethacrylate                                                                              --     40     20     10     --                              Diethylaminoethylmethacrylate                                                                   --     --     --     10     10                              4-Vinylpyridine   5      5      5      --     --                              Cyclohexylmethacrylate                                                                          15     15     --     --     --                              Acrylonitrile     --     --     15     --     --                          12. Polymerization Initiator                                                      AZDN.sup.5        3      2      3      3      3                               Cumene Hydroperoxide                                                                            --     2      --     --     3                           13. Polymerization Conditions                                                     Time, hours, approx                                                                             6      6      6      6      6                               Temperature, ° C.                                                                        80     80     80     80     80                              Conversion, approx. 100% (X)                                                                    X      X      X      X      X                           14. Intrachromoleucospheruloid                                                    Pigment Dispersion                                                            yield             960    960    960    960    960                             Average Particle Size                                                         Diameter (microns)                                                                              <4.0   <4.0   <4.0   <4.0   <4.0                        __________________________________________________________________________     *used as wet presscake material                                               **capable of effecting emulsion polymerization                                Unitane tradename for American Cyanamid titanium dioxide pigment              TiPure tradename for DuPont titanium dioxide pigment                          Aerosil tradename for Degussa Company pyrogenic silica                        .sup.1 sodium salt of a sulfate ester of an alkylphenoxy                      poly(ethyleneoxy)ethanol (28% active)                                         .sup.2 octylphenoxy polyethoxy ethanol (70% active)                           .sup.3 substituted imidazoline of tall oil (100% active)                      .sup.4 substituted imidiazoline quaternized with benzyl chloride (100%        active)                                                                       .sup.5 azobisisobutyronitrile                                            

EXAMPLES A et seq. Further Detailed Step-wise Procedures for ProducingIntrachromoleucospheruloid Pigment Composition in Various Forms

The following Examples are again given in detailed procedural form tofurther exemplify this invention.

Example A (Micronizing of organic and inorganic pigment material asseparate steps) Step 1 (Micronizing organic color pigment with acidicmonomer material present)

To a sand mill is charged 20 grams (dry basis) of Vat Green 1 (CI59825 - Ponsol Jade Green Presscake) and 10 grams (dry basis) of IrgazinYellow 2GLT (Pigment Yellow 109) together with 200 grams of water, 3grams methacrylic acid, 2 grams Tamol SN (sodium salt of a condensednaphthalene sulfonic acid), 2 grams Duponol ME (sodium lauryl sulfate)10 grams Alipal CO 433 (sodium salt of a sulfate ester of analkylphenoxy poly (ethyleneoxy) ethanol 28% active) and sufficientOttawa sand to grind the charge. The charge is milled until arepresentative sample under microscopic examination shows essentially novisible particulate organic material and hence has all of its particlesbelow 0.02 micron in diameter. The organic color pigment dispersion isthen separated from the grinding medium by screening and washing toyield 600 grams of color pigment dispersion.

Step 2 (Micronizing inorganic pigment material with basic monomermaterial present)

To a ball mill is charged 50 grams of titanium dioxide pigment (TiPureR900, DuPont), 20 grams of silica pigment (HiSil 233, PPG), 300 gramswater, 6 grams dimethylaminoethylmethacrylate, 20 grams Triton X405(octylphenoxy polyethoxy ethanol, 70% active) and 2 grams Tamol SN(sodium salt of a condensed naphthalene sulfonic acid). The charge ismilled until a representative sample under microscopic examination showsessentially all of the inorganic pigment material to be below 0.2 micronin diameter, i.e. titanium dioxide particles of less than 0.1 micronwith silica dioxide adhering to said titanium dioxide particles, thesaid composite particles being essentially all below 0.2 micron indiameter. The inorganic pigment dispersion is separated from thegrinding medium by screening and washing to yield 600 grams of inorganicpigment composition dispersion.

Step 3 (Combination "wedding" and polymerization step)

To an emulsion polymerization apparatus equipped with high speedstirring is charged 600 grams of the inorganic pigment dispersionprepared with cationic monomer and nonionic dispersant from step 2. Withvigorous agitation, 200 grams of the organic pigment dispersion preparedwith anionic monomer and a combination of anionic and nonionicdispersants from step 1 are added so that the anionic component combineswith the cationic component thus wedding the organic color pigment tothe inorganic pigment without breaking the dispersion. 100 grams of a20% aqueous solution of a copolymer of styrene, methacrylic acid andacrylonitrile (ratio 25/65/10, NH₄ OH salt) are added together with 60grams of a monomer mixture consisting of 20 grams styrene, 20 gramsmethylmethacrylate and 20 grams of 50% divinylbenzene and the system ispurged with nitrogen. The temperature of the reaction is raised to 45°C. and 21/2 grams of cumene hydroperoxide added. The reactiontemperature is raised rapidly to 70° C. and held there for 5 hours. Oncooling a bright green intrachromoleucospheruloid latex is obtained.Microscopic examination of a representative sample shows it to consistof bright green opaque spheruloids of polymer, cross-linked by virtue ofthe divinylbenzene used, to essential insolubility in all physicalsolvents. The product may be used as is for any purpose where such alatex is suitable, as in the coloration of aqueous based printingformulas, water based paint systems etc.

Example B (Soft powdering and drying)

The procedure of Example A is followed with the exception that thebright green latex is diluted with an equal volume of water andacidified to a pH of 5.0 with dilute aqueous acetic acid to coagulatethe product. 40 grams of a 10% solution of di-tertiary-octyl sodiumsulfosuccinate in Stoddard Solvent are added and the slurry heated withturbulent agitation to 80° C. and held there for 5 hours. The coagulumis separated, by filtration and washing, from the serum and then driedto give the bright green intrachromoleucospheruloid pigment in softpowder form suitable for use in oil based and thermoplastic systems aswell as for use in aqueously based systems which are of appropriaterefractive index.

Example C (Product substantive to cellulosic materials and glass)

The procedure of Example B is followed with the exception that in thepolymerization step, after the addition of the polymeric surface activeagent material (copolymer of styrene/methacrylic acid/acrylonitrile),but prior to the addition of the monomer material, is added 20 grams ofa water soluble polyethylenimine PEI 600 (Dow). This yields anintrachromoleucospheruloid pigment composition having polyethyleniminetherein. This composition has increased affinity for cellulosicsubstrate and glass fibre materials especially when used in printingformulations.

Example D (Sequential polymerization of monomers)

The procedure of Example A is followed with the exception that in thepolymerization step the monomer material is sequentially added; thefirst addition consisting of a mixture of 20 grams of styrene and 15grams of methylmethacrylate and that after the initial polymerization at70° C. for 5 hours the reaction is cooled to 45° C. and thecross-linking monomer material consisting of a mixture of 5 grams ofmethylmethacrylate and 20 grams of 50% divinylbenzene are then added.The reaction is then stirred for 20 minutes to allow this additionalmonomer material to be absorbed into the noncross-linkedintrachromoleucospheruloids, and then heated to 75°-80° C. and heldthere for an additional 5 hours to complete the polymerization of saidabsorbed cross-linking monomer material, thus producingintrachromoleucospheruloid pigment in cross-linked form, suitable forfurther processing, e.g. soft powder treatment, coagulation and drying.

OTHER EXAMPLES

It was shown e.g. in Example D that the spheruloids of the compositionmay be produced initially as noncross-linked particles, and bethereafter cross-linked by absorbing cross-linking monomer thereinto andsubjecting the same to further polymerization. It has thus been shownthat any of the noncross-linked products exemplified may be prepared incross-linked form by the concurrent or sequential polymerizationtherewith of cross-linking monomers.

Since the criteria common to the noncross-linked and cross-linkedembodiments of the invention are that the products be insoluble in thevehicle of intended use and have a different refractive index than thelatter, it will be apparent from the foregoing that the cross-linkingmonomers, in the Examples producing cross-linked products, may also bereplaced by noncross-linking monomers, where the criteria will besatisfied by the environment of use.

While there have been described herein what are at present consideredpreferred embodiments of the invention, it will be obvious to thoseskilled in the art that modifications and changes may be made thereinwithout departing from the essence of the invention. For example, themicronized materials in liquid media may be stored after preparation,especially if they contain adequate emulsifier, such previously preparedmicronized dispersions may be blended, preferably under furthermicronization, to provide in liquid media micronized mixed pigments forthe process; the modes of combining, heating and polymerizing theingredients may be varied dependent upon the volumes of materials beinghandled in manners known to those skilled in the emulsion polymerizationart; etc. It is therefore understood that the exemplary embodiments areillustrative and not restrictive of the invention, the scope of which isdefined in the appended claims, and that all modifications that comewithin the meaning and range of equivalents of the claims are intendedto be included therein.

This application is one of the following series of applications:

    ______________________________________                                              Case                                                                    Num-  Num-    Serial                                                          ber   ber     Number   Title                                                  ______________________________________                                        First 90-A    712,257  Intrachromospheruloid Pigments                                                and Processes for Producing Same                       Second                                                                              90-B    712,254  Intraleucospheruloid Pigments                                                 and Processes for Producing Same                       Third 90-C    712,255  Intrachromospheruloid/Inorganic                                               Pigment Compositions and Processes                                            for Producing Same                                     Fourth                                                                              90-D    712,256  Intraleucospheruloid/Organic Color                                            Pigment Compositions and Processes                                            for Producing Same                                     Fifth 90-E    712,252  Intrachromospheruloid/Intraleuco-                                             spheruloid Pigment Compositions                                               and Processes for Producing Same                       Sixth 90-F    712,253  Intrachromoleucospheruloid Pigment                                            Compositions and Processes for                                                Producing Same                                         ______________________________________                                    

All of the cases of this series are herein incorporated by reference.The titles of the respective cases indicate the lines of divisionbetween the subjects matter thereof. Thus the product of the first caseconsists essentially of transparent emulsion polymer particles,preferably cross-linked to insolubility in physical solvents and havingprimary particles of colloidal size (spheruloids), enhancing the opticalproperties of still smaller particles of organic color pigment (chromopigment) embedded within them (intra). The second case, in lieu of theorganic color pigment has embedded within its spheruloids inorganicwhite pigment (leuco pigment) enhanced thereby. The product of the thirdcase is a special combination of intrachromospheruloid pigment affixedto leuco pigment and coloring the light reaching and reflected from thelatter. The product of the fourth case is a special combination ofintraleucospheruloid having chromo pigment material affixed thereto andilluminating the same. The product of the fifth case is a specialcombination of intrachromospheruloid and intraleucospheruloid pigmentsbonded together giving mutually enhanced tinctorial properties. Theproduct of the sixth case differs from the foregoing in that itsspheruloids have embedded therein and enhance the tinctorial effects ofcomposite particles of essentially transparent organic color (chromo)and inorganic white (leuco) components wedded to each other.

Also incorporated by reference herein are our copending applicationsSer. No. 712,213 and 712,160 (Cases 88 and 89) filed concurrentlyherewith and respectively entitled "Improved Vinylic Filler Products andProcesses for Producing Same" and "Improved Vinylic Filler Pigments andProcesses for Producing Same", which copending applications apply tomaterials different from those concerned in the above listed series ofapplications, i.e. non-intrachromo- and non-intraleuco- pigmentmaterials, the applicants' soft powdering techniques constituting partsof certain combinations disclosed and claimed in the presentapplication.

We claim:
 1. A process for producing insolubleintrachromoleucospheruloid pigment composition, which process comprises,in combination:(a) providing in liquid medium a composite chromoleucopigment composition consisting essentially of particles of organic colorpigment composition wedded to particles of inorganic leuco pigmentcomposition; said chromoleuco pigment composition being dispersed insaid liquid medium with the aid of 0-100% by weight of the total ofsurface active agent material set forth in (c) and the weight ratio ofsaid organic color pigment composition to said inorganic pigmentcomposition therein lying in the range of 100:1 to 1:100, dry basis;said organic color pigment composition having primary particles of anaverage size less than 0.2 micron in diameter and being essentiallyinsoluble in said liquid medium and said inorganic pigment compositionhaving primary particles of an average size less than 0.2 micron indiameter and being selected from the class consisting of the inorganicopaque white pigments and the inorganic transparent white pigmentshaving refractive indicies different from that of the cross-linkedorganic polymer produced by step (d), and combinations of any two ormore of the foregoing, (b) forming an aqueous emulsion polymerizationsystem consisting essentially of (i) the composition of (a), (2) thebalance, if any, of 100% of the total of surface active agent materialset forth in (c), (3) monomer material selected in the ratio of saidmonomer material to said composite pigment composition lying in therange of 100:1 to 1:20 by weight and (4) emulsion polymerizationinitiator in an effective amount in the range of 0.2 to 10% by weight ofthe said monomer material; said monomer material being ethylenicallyunsaturated monomer material selected from the class consisting of (i)monomer material polymerizable through a single ethylenicallyunsaturated group in the amount of 0% to 99.8% by weight of the totalmonomer material and (ii) monomer material polymerizable through aplurality of ethylenically unsaturated groups in an amount, in the rangeof 0.2 to 100% by weight of the total monomer material, sufficient toproduce polymer cross-linked to essential insolubility in any physicalsolvent, (c) the ratio of the total of the surface active agent materialpresent after (b) to said composite pigment composition and monomermaterial lying in the range of 2:1 to 1:40 by weight and said total ofsurface active agent material being selected from the class of polymericand nonpolymeric surface active agents and combinations thereof capableof effecting emulsion polymerization of the selected ethylenicallyunsaturated monomer material to yield polymer particles with thecomposite pigment composition provided in step (a), embedded therein,(d) effecting emulsion polymerization of the combination formed in (b)under agitation and at sufficient temperatures in the range of 0° to200° C. for sufficient time in the range of a few minutes to 24 hours topermit the polymerization to proceed far enough in the range from 50 to100% conversion by weight of said monomer material to produce in aqueousdispersion an intrachromoleucospheruloid pigment composition consistingessentially of spheruloids of organic polymer material cross-linked toessential insolubility in any physical solvent, having primary particlesof an average size not exceeding 4 microns in diameter, and havingembedded therein the still smaller size particles of said compositechromoleuco pigment composition, and (e) recovering saidintrachromoleucospheruloid pigment composition.
 2. A process as claimedin claim 1, in which the ratio in step (c) is selected to produceintrachromoleucospheruloid pigment dispersion in step (d) in the form ofa latex.
 3. A process according to claim 1, in which the ethylenicallyunsaturated monomer material in step (b) comprises several portionssequentially added and sequentially polymerized in step (d), at leastone of said several portions comprising monomer material polymerizablethrough at least two ethylenically unsaturated groups in a sufficientproportion to cross-link the polymer of the intrachromoleucospheruloidsto essential insolubility in any physical solvent.
 4. A processaccording to claim 1, in which the monomer material in step (b) having aplurality of polymerizable ethylenically unsaturated groups consistsessentially of material copolymerizable with vinyl monomers and selectedfrom the unsaturated conjugated drying oils and their acids andderivatives of the foregoing, the ratio of said drying oil material tothe other monomer material in step (b) lying in the range of 0.2:99.8 to20:80 by weight.
 5. A process according to claim 1, wherein at least oneof the organic and inorganic pigment compositions supplied for step (a)is a relatively coarse particulate pigment composition and in step (a)is micronized in the liquid medium with the aid of any surface activeagent present therein until said pigment composition has primaryparticles of an average size less than 0.2 micron in diameter.
 6. Aprocess according to claim 1, wherein said organic and inorganic pigmentcompositions supplied for step (a) are co-micronized in said liquidmedium in effecting the wedding of the particles thereof to form saidcomposite pigment composition.
 7. A process according to claim 6,wherein the liquid medium provided in step (a) consists essentially ofan aqueous solution of from 1% to 10% by weight of the total of surfaceactive agent set forth in (c).
 8. A process according to claim 6,wherein the liquid medium provided in step (a) consists essentially ofmonomer material employed in step (b), and in which the surface activeagent material employed in step (b) is dissolved in sufficient water toform the emulsion polymerization system of step (b).
 9. A processaccording to claim 6, wherein co-micronizing is effected with the aid ofat least 2% by weight, based on the inorganic pigment compositiontherein, of pigment bonding agent material.
 10. A process according toclaim 6, wherein the co-micronizing is effected in aqueous mediumcontaining at least 2% by weight of the monomer material employed instep (b), based on the inorganic pigment composition present.
 11. Aprocess according to claim 10, wherein the said 2% by weight of monomermaterial consists essentially of amine monomer material.
 12. A processaccording to claim 1, in which the surface active agent materialemployed in (b) comprises polymeric and nonpolymeric surface activeagent.
 13. A process according to claim 12, in which said polymericsurface active agent has acidic groups at least in part in the form ofwater soluble salts.
 14. A process according to claim 12, in which saidpolymeric surface active agent has basic groups at least in part in theform of water soluble salts.
 15. A process according to claim 12, inwhich said polymeric surface active agent has both acidic and basicgroups at least in part in the form of water soluble salts.
 16. Aprocess according to claim 1, wherein step (e) is practiced bycoagulating the intrachromoleucospheruloid pigment produced by step (d),and separating serum from the coagulum to provide theintrachromoleucospheruloid pigment composition as wet coagulum.
 17. Aprocess according to claim 1, wherein step (e) is practiced bycoagulating the intrachromoleucospheruloid pigment produced by step (d),separating serum from the coagulum, and drying the wet coagulum.
 18. Aprocess according to claim 1, wherein (f) as a part of step (e) theinsoluble intrachromoleucospheruloid pigment composition produced inaqueous dispersion in step (d) is modified to contain, per 100 partsthereof, dry basis by weight, from 0.5 to 35 parts of soft powderingagent.
 19. A process according to claim 18, which further comprises (g)as a part of step (e), after step (f), drying the modified compositionto obtain the intrachromoleucospheruloid pigment composition in softpowder form.
 20. A process according to claim 18, which furthercomprises (g) as a part of step (e), after step (f), spray drying themodified composition to obtain the intrachromoleucospheruloid pigmentcomposition in particulate soft powder form.
 21. A process according toclaim 1, in which the inorganic pigment composition in step (a) consistsessentially of silica pigment composition and titanium dioxide pigmentcomposition in a weight ratio in the range of 1:10 to 10:1.
 22. Aprocess according to claim 1, in which(I) the inorganic pigmentcomposition is selected from the class consisting of the followinggroups (1) siliceous pigment compositions selected from (i) the naturalsilica pigments, (ii) the precipitated silica pigments, (iii) thepyrogenic silica pigments, (iv) the alkaline-earth metal silicatepigments, (v) the aluminum silicate pigments, (vi) the zinc silicatepigments, (vii) the zirconium silicate pigments and (viii) combinationsof any two or more of the foregoing; (2) titanium dioxide pigmentcompositions; (3) pigment compositions selected from the classconsisting of the following groups (i) alkaline-earth metal carbonateand sulfate pigments (ii) alumina pigments, (iii) hydrated aluminumoxide pigments, (iv) antimony oxide pigments, (v) zinc oxide pigments,(vi) zironium oxide pigments and (vi) combinations of any two or more ofthe foregoing, and (4) combinations of any two or more members selectedrespectively from groups of (1), (2) and (3).
 23. A process according toclaim 22, in which the selected inorganic pigment composition consistsessentially of siliceous pigment of said groups (1)(ii) and (1)(iii).24. A process according to claim 1, in which the inorganic pigmentcomposition in step (a) consists essentially of titanium dioxide pigmentcomposition having primary particles of an average size in the range ofabout 0.2 to 0.1 micron in diameter.
 25. A process according to claim 1,in which the inorganic pigment composition in step (a) consistsessentially of titanium dioxide pigment composition having primaryparticles of an average size less than 0.2 micron in diameter.
 26. Aprocess according to claim 1, in which:said composite pigmentcomposition contains from 0 to an equal weight of pigment bonding agentmaterial, based on the inorganic pigment material therein, selected fromthe class consisting of (i) water soluble alkali metal silicatesprecipitated in the presence of at least a part of the pigmentcomposition, (ii) water soluble titanium compounds precipitated in thepresence of at least a part of the pigment composition, (iii) watersoluble and dispersible aminoplasts preformed and formed in situ andadhered to at least a part of the pigment composition, (iv) watersoluble and dispersible phenoplasts preformed and formed in situ andadhered to at least a part of the pigment composition, (v) water solubleand dispersible organic polymers having carboxyl, amine, sulfate andsulfonic acid groups and salts thereof precipitated in the presence ofat least a part of the pigment composition, and (vi) water soluble anddispersible organic silanes; and said composite pigment composition hasfrom 0 to an equal weight of nitrogenous material therewith based on theinorganic pigment material therein, said nitrogenous material beingselected from the class consisting of (i) oleophilic amines, (ii)oleophilic imines, (iii) oleophilic amine carboxylates, (iv) theoleophilic quaternary ammonium compounds, (v) water soluble polyamines,(vi) water soluble imines, and (vii) combinations of two or more membersof the foregoing.
 27. An insoluble intrachromoleucospheruloid pigmentconsisting essentially of spheruloids of organic polymer materialcross-linked to essential insolubility in any physical solvent, saidpolymer material consisting essentially of polymerized monomer materialselected from the class consisting of the monoethylenically unsaturatedand polyethylenically unsaturated polymerizable compounds, and saidspheruloids having primary particles of an average size not exceeding 4microns in diameter, which have embedded therein still smaller particlesof composite pigment composition, said composite pigment compositioncomprising, as component particles thereof, organic color pigmentmaterial and inorganic leuco pigment material, wedded to each other, theweight ratio of said organic polymer material to said composite pigmentcomposition being in the range of 100:1 to 1:20, the organic colorcomponent of said composite pigment material having primary particles ofan average size not exceeding 0.2 micron in diameter, the inorganicleuco component of said composite pigment material being selected fromthe class consisting of the opaque white pigments and the transparentwhite pigments having refractive indicies different from that of thecross-linked organic polymer of the speruloids and having primaryparticles of an average size not exceeding 0.2 micron in diameter, andthe weight ratio of said organic color component to said inorganic leucocomponent of said composite pigment material being in the range of 100:1to 1:100 by weight.
 28. An intrachromoleucospheruloid pigment accordingto claim 27 in the form of a latex.
 29. An intrachromoleucospheruloidpigment according to claim 27, in the form of a wet coagulum.
 30. Anintrachromoleucospheruloid pigment according to claim 27, in powderform.
 31. An intrachromoleucospheruloid pigment according to claim 27,in soft powder form.
 32. An intrachromoleucospheruloid pigmentcomposition according to claim 27, in which the inorganic component ofsaid composite pigment material consists essentially of silica pigmentcomposition and titanium dioxide pigment composition in a weight ratioin the range of 1:10 to 10:1.
 33. An intrachromoleucospheruloid pigmentcomposition according to claim 27, the inorganic component of saidcomposite pigment composition being selected from the class consistingof the following roups (1) siliceous pigment compositions selected from(i) the natural silica pigments, (ii) the precipitated silica pigments,(iii) the pyrogenic silica pigments, (iv) the alkaline earth silicatepigments, (v) the aluminum silicate pigments, (vi) the zinc silicatepigments, (vii) the zirconium silicate pigments, and (viii) combinationsof any two or more of the foregoing; (2) titanium dioxide pigmentcompositions; (3) metal oxide and hydroxide pigment compositionsselected from (i) alkaline-earth oxide pigments, (ii) alumina pigments,(iii) aluminum hydroxide pigments, (iv) antimony oxide pigments, (v)zinc oxide pigments, (vi) zirconium oxide pigments, and (vii)combinations of any two or more of the foregoing, and (4) combinationsof any two or more members selected respectively from groups (1), (2),and (3); the composite pigment composition thereof containing from 0 toan equal weight of pigment bonding agent material formed in situ in thepresence of at least the inorganic component of said pigmentcompositions, and selected from the class consisting of water insolubledeposits from (i) water soluble alkali metal silicates, (ii) watersoluble titanium compounds, (iii) water soluble and dispersibleaminoplasts preformed and formed in situ, (iv) water soluble anddispersible phenoplasts preformed and formed in situ, (v) water solubleand dispersible organic polymers having carboxyl, amine, sulfate andsulfonic acid groups and salts thereof, and (vi) water soluble anddispersible organic silanes; and the composite pigment compositionthereof having from 0 to an equal weight of nitrogenous materialtherein, said nitrogenous material being selected from the classconsisting of (i) oleophilic amines, (ii) oleophilic amines, (iii)oleophilic amine c carboxylates, (iv) the oleophilic quaternary ammoniumcompounds, (v) water soluble polyamines, (vi) water soluble imines, and(vii) combinations of two or more members of the foregoing.
 34. Anintrachromoleucospheruloid pigment composition according to claim 33, inwhich the inorganic component of said composite pigment compositionconsists essentially of silica pigment composition of the group havingprimary particles of an average size in the range of 0.2 to 0.01 micronin diameter.
 35. An intrachromoleucospheruloid pigment compositionaccording to claim 27 in which the inorganic pigment material consistsessentially of titanium dioxide pigment composition having primaryparticles of an average size of less than 0.2 micron in diameter.
 36. Anintrachromoleucospheruloid pigment composition according to claim 27, inwhich the inorganic pigment material consists essentially of titaniumdioxide pigment composition having primary particles of an average sizein the range of about 0.2 to 0.1 micron in diameter.
 37. Anintrachromoleucospheruloid pigment material according to claim 27, inwhich the organic color pigment material embedded in the polymermaterial consists of an essentially homogenous mixture of two or morechemically different organic color pigments, saidintrachromoleucospheruloid pigment exhibiting a coloration differentfrom that of either of said color pigments.